MXPA00003511A - Mid-chain branched surfactants with cellulose derivatives - Google Patents

Abstract

The present invention relates to detergent compositions, for example those useful for laundering fabrics, washing dishes, or cleaning hard surfaces, comprising:at least about 0,5%of a longer alkyl chain, mid-chain branched surfactant compounds;and from about 0,001%to about 10%, by weight, of a cellulose derivative.

Description

SURGICAL SURGICAL AGENTS IN YOUR MEDIA CHAIN. WITH CELLULOSE DERIVATIVES FIELD OF THE INVENTION The present invention relates to detergent compositions comprising a selected amount of a cellulose derivative and branched surfactants in the middle region of its chain. These branched surfactants in the middle region of their chain are mixtures of branched surfactants in the middle region of their longer alkyl chain derived from hydrophobic groups of branched primary alkyl in the middle region of their chain and selected hydrophilic groups, said blends comprising hydrophobic groups of primary alkyl branched in the middle region of your chain that have an average of more than 14.5 carbon atoms, preferably more than about 15 carbon atoms, the preferred surfactants of the present being the primary alkylsulphate surfactants branched in the middle region of their chain and the branched primary alkoxylated alkylsulfate surfactants the middle region of its chain.

In this way, the present invention relates to a combination of cellulose derivatives and mixtures of branched surfactants in the middle region of their chain useful in cleaning and laundry compositions, especially granular or liquid detergent compositions.

BACKGROUND OF THE INVENTION Conventional detersive surfactants comprise molecules having a water-soluble substituent (hydrophilic group) and an oleophilic substituent (hydrophobic group). Such surfactants typically comprise hydrophilic groups such as carboxylate, sulfate, sulfonate, amine oxide, polyoxyethylene and the like, attached to a hydrophobic alkyl, alkenyl or alkalyl group typically containing between about 10 and about 20 carbon atoms. Accordingly, the manufacturer of said surfactants must have access to a source of hydrophobic groups to which the hydrophilic group can be linked by chemical means. The first source of hydrophobic groups comprised natural fats and oils, which were converted to soaps (ie hydrophilic carboxylate group) by saponification with base. Coconut oil and palm oil are still used to make soap, as well as to make the alkyl sulfate ("AS") class of surfactants. Other hydrophobic groups are available from petrochemicals, including alkylated benzene, which is used to make alkylbenzene sulfonate ("LAS") surfactants. The literature points out that certain branched hydrophobic groups can be used to improve the manufacture of alkyl sulfate detersive surfactants; see, for example, US 3,480,556 to DeWitt et al., November 25, 1969. However, it has been determined that the beta-branched surfactants described in the '556 patent are inferior with respect to certain solubility parameters, as is evident by its Krafft temperatures. It has further been determined that surfactants having branching towards the center of the carbon chain of the hydrophobic group have much lower Krafft temperatures. See "The Aqueous Phase Behavior of Surfactants", R.G. Laughiin, Academic Press, N.Y. (1994) p. 347. Accordingly, it has now been determined that such surfactants are preferred to be used especially under washing conditions with fresh or cold water (eg, 20 ° C-5 ° C). Generally, alkyl sulphates are well known to those skilled in the art of detersive surfactants. The alkyl sulfates are developed as a functional improvement over traditional soap surfactants, and have been found to possess improved solubility and surfactant characteristics. Linear alkyl sulphates are the most commonly used alkyl sulfate surfactants and are the easiest to obtain. For example, linear long chain alkyl sulphates, such as tallow alkyl sulfate in laundry detergents have been used. However, these have significant limitations in cleaning performance, especially with the tendency to lower wash temperatures. Similarly, as mentioned before, branched 2-alkyl or "beta" alkyl sulfate is known. In addition to E.U.A. 3,480,556 mentioned above, EP 439,316, published July 31, 1991 and EP 684,300, published on November 29, 1995, more recently, describe these beta-branched alkyl sulphates. Other recent scientific papers in the area of branched alkyl sulfates include R. Varadaraj and others, J. Phys. Chem., Vol. 95, (1991), pp 1671-1676, which detects the surface stresses of a variety of agents "linear of Guerbet" and "ramified Guerbet" surfactants including alkylsulfates. The "linear types of Guerbet" are essentially "Y-shaped", with ramification of position 2 which is a long straight chain as in: where Z is, for example, OS03Na. Lps "branched Guerbet" types are likewise branched at position 2, but they also have additional branching substitution, as in: where Z is, for example, OS03Na. See also Varadaraj et al., J. Colloid and Interface Sci., Vol. 140, (1990), pp 31-34 which relates to foaming data for surfactants including C12 and C13 alkyl sulfates containing 3 and 4 methyl branches, respectively (see 5 especially p.32). The known alkyl sulphates also include: 1. Primary alkylsulphates derived from alcohols made by reaction of Oxo in propylene or n-butylene oligomers, for example as described in U.S. Patent 5,245,072, assigned to Mobil.

Corp. 2. The primary alkyl sulphates derived from lipids containing oleic acid, for example the so-called "isostearyl" types, see EP 401, 462 A, assigned to Henkel, published on December 12, 1990, which describes certain isostearyl alcohols and ethoxylated isostearyl alcohols and their Sulfation to produce the corresponding alkyl sulfates such as sodium isostearylsulfate. 3. The primary alkyl sulphates, for example the so-called "tridecyl" types derived from oligomerizing propylene with an acid catalyst followed by Oxo reaction. 4. Primary alkylsulphates derived from "Neodol" or "Dobanol" processing alcohols: these are Oxo products of linear internal olefins or are Oxo products of linear alpha-olefins. Olefins are derived by oligomerization of ethylene to form alpha-olefins that are used directly or that are somerized to internal olefins and metatesized to give internal olefins of different chain lengths; 5. Primary alkylsulphates derived from the use of "Neodol" or "Dobanol" catalysts in internal olefins derived from supply materials that are different from those normally used to manufacture "Neodol" or "Dobanol" alcohols, deriving the internal olefins from dehydrogenation of petroleum paraffins; 6. The primary alkylsulphates derived from the conventional Oxo reaction (eg, catalyzed with high pressure cobalt) of internal olefins, the internal olefins being derived from the dehydrogenation of petroleum paraffins; 7. The primary alkylsulphates derived from the conventional Oxo reaction (eg, catalyzed with high pressure cobalt) of alpha-olefins; 8. The primary alkyl sulphates derived from natural linear fatty alcohols such as those commercially available from Procter & Gamble Co .; 9. The primary alkyl sulphates derived from Ziegler alcohols such as those commercially available from Albermarle; 10. The primary alkyl sulphates derived from the reaction of normal alcohols with a Guerbet catalyst (the function of this well known catalyst is to dehydrogenate two moles of normal alcohol to the corresponding aldehyde, to condense them in a condensation with aldol and to dehydrate the product which is an alpha-, beta-unsaturated aldehyde which is then hydrogenated to the 2-alkyl branched primary alcohol, all in a "reaction vessel"); 11. The primary alkyl sulphates derived from the dimerization of sobutylene to form 2,4,4'-trimethyl-1-pentene, which in the reaction of Oxo to the aldehyde, dimerization with aldol, dehydration and reduction produces alcohols; 12. The secondary alkyl sulfates derived from the addition of sulfuric acid to alpha-olefins or internal olefins; 13. The primary alkylsulphates derived from the oxidation of paraffins by the steps of (a) oxidizing the paraffin to form a fatty carboxylic acid and (b) reducing the fatty carboxylic acid to the corresponding primary alcohol; 14. The secondary alkyl sulfates derived from the direct oxidation of paraffins to form secondary alcohols; 15. The primary or secondary alkyl sulphates derived from various plasticizing alcohols, typically by the Oxo reaction of an olefin, condensation with aldol, dehydration and hydrogenation (example of conventional Oxo catalysts are the Co catalysts, or more recently, the Rh catalysts ); and 16. Primary or secondary alkyl sulfates that are not of the linear primary type, for example, phytol, famesol, isolated from sources of natural products.

However, apart from said known alkyl sulphates, there is a vast array of other possible alkyl sulfate compounds and mixtures, whose physical properties may or may not make them useful as detergent surfactants for laundry. Structures (l) - (XI) show only some of the possible variations (salts are shown only as common sodium salts).

CH, I 3 (CH 2) C CH, I 3 CH 3 (CH 2) to CH 2 OS 0 3 N a CH 3 (CH 2) b CHCH 2 OS 0 3 N a CH 3 (CH 2) d CH (CH 2) e CH 2 OS O 2 Na IV V CH3 OH, (? 2> m OS03Na CH3 (CH2) kCH (CH2) | CH CH2 OS03Na CH3 (CH2) nCH (CH2) CH3 VI Vil C, H3o C | H 3o C, H3Q C, H3O H3? H3 CH, CH, CH3CH (CH2) 3CH (CH2) 3CH (CH2) 3CH (CH2) 2OS03Na C H C C HoC HC H C H2C HC HC H C C Ho CH, CH, CH, I 2 OS03Na VIII IX 14 XI XII XIII These structures are also useful to illustrate the terminology in this field: in this way, (I) is a "linear" alkylsulfate. (I) is also a "primary" alkyl sulfate, in contrast to (Vil) which is a "secondary" alkylsulfate. (II) is also a "primary" alkyl sulfate but is "branched". The branching is exclusively in "position 2" as in the so-called "linear Guerbet" alkyl sulfates: the carbon count by convention starts with C1, which is the carbon atom covalently bound to the sulphate portion. (III) can be used to represent any of a series of branched alkyl sulphates which, when e is an integer having the value 1 or more, have only "branching not in position 2". According to conventional knowledge, at least for linear surfactant compounds, the hydrocarbon portion needs to have at least 12 carbon atoms, preferably more, to obtain adequate detergency. The indices a, b, c, d, e, f, g, h, i, j, k, I, m, n, o, p, q can, in principle, be adjusted to satisfy this need. The compound (VIII) is the alkyl sulfate derived from a naturally occurring branched alcohol, phytol. The compound (IX) is a highly branched alkyl sulfate which can, for example, be made by sulfating an alcohol derived from the dimerization of sobutylene and carrying out an Oxo reaction in the product. The compound (X), when q = 14, is an isostearyl alkyl sulfate; another so-called alkylsulfate "of isostearyl" has the general structure (III); said compounds can be made by sulfating an alcohol derived from a monomeric byproduct of the dimerization of oleic acid having 18 carbon atoms, ie, d + e = 14 in (III). The compound (XI) is a "neo" alkyl sulfate. (XII) and (XIII) are structures that illustrate "neighbor" dimethyl branch (XII) and "geminate or" gem "(XIII), respectively, said structures can, in principle, occur in alkyl sulfate and other surfactants. The conventional alkylsulphates can be saturated or unsaturated.Sodium oleyl sulfate, for example, is a saturated alkylsulfate.Sunsaturated alkyl sulphates such as oleumsulfate can be relatively expensive and / or relatively incompatible with detergent formulations, especially those containing bleach. In addition to the above structural variations, highly branched and complex primary alkyl sulfate mixtures having quaternary carbon atoms in the hydrophobic group can be produced, for example by sulfation of an Oxo alcohol made by means of the catalysed polysaccharide reaction. with acid, in addition stereoisomerism, possible in many branched alkyl sulphates, multiplies plus the number of species; and the commercial alkyl sulfates may contain impurities including the corresponding alcohols, inorganic salts such as sodium sulfate, hydrocarbons and cyclic by-products of their synthesis. A known material is sodium isostearyl sulfate, which is a mixture of methyl and / or ethyl branches distributed along a linear alkyl base structure in which the total number of carbons in the complete molecule is about 18. This " 'mix' is prepared in low yield from sourcing materials from natural sources (ie, tallow oil, soy, etc.) by a procedure that results in a branching that occurs in an uncontrolled manner, and that may vary depending on the source of the supply material. EP 401,462, assigned to Henkel and published on December 12, 1990, discloses certain isostearyl alcohols and ethoxylated isostearyl alcohols and their sulfation to produce the corresponding alkyl sulphates, such as "sodium isostearylsulfate" (CAS 34481-82-8 , sometimes called "sodium isooctadecyl sulfate"). Again, although R.G. Laughiin in "The Aqueous Phase Behavior of Surfactants", R.G. Laughiin, Academic Press, N.Y. (1994) p. 347 describes the observation that as the branching moves away from the 2-alkyl position towards the center of the hydrophobic alkyl group, there is a decrease in the Krafft temperatures (for a 15% solution), said solubility observations teach nothing about the tensioactive capacity of these compounds or their usefulness for incorporation in detergent compositions. In fact, both the commercial practice and the published literature are equivocal in the desire to ramify the region of the middle chain. This includes the aforementioned patent publications which describe the beta-branched alkyl sulfates as the desired branching, as well as 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) or Technical Bulletin, Shell Chemical Co., SC: 364-80. These references indicate, with respect to the harmful structural changes in alcohol sulphates, that "moving to CH3 has an insignificant effect". The data presented in one table show a decrease in cotton detergency of 29% and a decrease in foam formation of 77% relative to the primary unbranched alcohol sulfate in the C13 chain length. In addition, JP 721232 discloses a negative detergency for the replacement of C11 linear primary alkyl sulfate with branched primary alkyl sulfate of unspecified branching. In addition, K.R. Wormuth and S. Zushma, Langmuir, Vol. 7, (1991), pp. 2048-2053 describes technical studies on a number of branched alkyl sulphates, especially the "branched Guerbet" type, derived from the highly branched "Exxal" alcohols made by Exxon. The phase studies establish a lipophilic index, ie a hydrophobic index, as follows: highly branched = double-tail >; branched methyl > linear. Suitably, branched surfactants mix oil and water less effectively than linear surfactants. The efficiency index is linear > double tail »methyl branched = highly branched. From these results, it is not immediately apparent what direction to take in the development of further improvements in branched alkyl sulfates. Thus, beyond simple technical theories about how to achieve superiority of cleanliness of one pure surfactant compound against another, the formulator and creator of surfactants for laundry detergents must consider a wide variety of possibilities with limited information (some sometimes inconsistent), and then strive to provide overall improvements in one or more of a wide range of criteria, including performance in the presence of complex mixtures of surfactants, trends at low wash temperatures, changes in formulation including builders, enzymes and bleaches, several changes in consumer habits and practices, and the need for biodegradability. In the context provided by these preliminary annotations, the development of improved alkyl sulphates for use in laundry detergents and cleaning products is clearly a complex challenge. Especially under washing conditions with fresh or cold water (for example, 20 ° C-5 ° C), the preferred long chain alkyl sulfate compositions probe combination of two p plus these branched primary alkyl sulfate surfactants in the middle region of its chain that provides a surfactant mixture that is higher in surfactant capacity and has better water solubility at low temperatures than any single branched alkyl sulfate. Mixtures such as those produced comprise the branching in the middle region of the desirable chain for use in the surfactant mixtures of the present invention or the surfactant mixtures described herein may be formulated by mixing the desired amounts of branched surfactants in the present invention. the middle region of your individual chain. Said higher blends are not limited to combinations with other branched surfactants in the middle region of their chain, but (preferably) can be combined in a suitable manner with one or more different conventional detergent surfactants (eg, other primary alkyl sulphates; alkylbenzene sulphonates; linear, ethoxylated alkyl sulphates, nonionic surfactants, etc.) to provide improved surfactant systems. These branched surfactants in the middle region of their chain are obtained at a relatively high purity, making their effective commercialization in terms of costs for the formulator. Suitable product mixtures can be obtained from processes using fossil fuel sources. (The terms "derived from fossil fuels" or derived from "fossil fuel" are used herein to distinguish "synthetic" surfactants from coal, natural gas, petroleum oil and other "synthetic" surfactants derived from petrochemicals, from the which are derived from living natural sources such as cattle or plants such as coconut palms). Such a process is designed to provide branched reaction products that are primarily (85% or more) alpha-olefins, and which are then converted to a hydrophobic group in an Oxo reaction sequence. Said branched alpha-olefins contain from about 11 to about 18 (average) total carbon atoms and comprise a linear chain having an average length in the region 10-18. The branching is predominantly mono-methyl, but some di-methyl or ethyl branching may occur. Advantageously, said method results in very little (1% or less) geminal branching, that is, very little, if any, replacement of the "quaternary" carbon. Furthermore, very little (less than approximately 20%) neighborhood branching occurs. Of course, a part (ca. 20%) of the supply material used in subsequent Oxo processes may remain unbranched. Typically, and preferably from the viewpoint of cleaning performance and biodegradability, this procedure provides alpha-olefins with: an average number of branches (based on the longest chain) on the scale of 0.4-2.5; of the branched material, there is essentially no branching at the carbons 1, 2 or at the terminal (omega) carbon of the longer chain of the branched material. Following the formation and purification of the branched-chain alpha-olefin, the supply material is subjected to an Oxo carbonylation process. In this Oxo step, a catalyst (e.g., conventional cobalt carbonyl) is used which does not move the double bond from its initial position. This prevents the formation of vinylidene intermediates (which ultimately produce less favorable surfactants) and allows the carbonylation to proceed at carbon # 1 and # 2 atoms. Unexpectedly it has been determined that detergent compositions comprising a selected amount of a cellulose derivative in combination with branched surfactant compounds in the middle region of its long chain alkyl chain provide cleaning compositions having one or more advantages, including a higher surfactant capacity at low temperatures of use, improved resistance to water hardness, higher efficiency in surfactant systems, improved removal of greasy or body dirt from the fabrics, improved compatibility with detergent enzymes and the like. In particular, the combination of the branched surfactant in the middle region of its chain with a selected amount of cellulose derivative unexpectedly provides greater whiteness maintenance benefits as well as improved dirt release from fabrics, particularly cotton fabrics. / PREVIOUS TECHNIQUE The document E.U.A. No. 3,480,556 to DeWitt et al., November 25, 1969, EP 439,316, published by Lever on July 31 and EP 684,300, published by Lever on November 29, 1995, describe beta-branched alkyl sulphates. EP 439,316 discloses certain laundry detergents comprising a commercial and specific C14 / C15 branched primary alkyl sulfate, namely LIAL 145 sulfate. It is believed that it has 61% branching at the 2-position; 30% of this includes branching with a hydrocarbon chain having four or more carbon atoms. US-A-3,480,556 discloses mixtures of 10 to 90 parts of a straight chain primary alkylsulfate and 90 to 10 parts of a beta-branched primary alcohol sulfate (branched at position 2) of the formula: wherein the total number of carbon atoms varies from 12 to 20 and R1 is a straight chain alkyl radical containing 9 to 17 carbon atoms and R2 is a straight chain alkyl radical containing 1 to 9 carbon atoms (ramifications 67% 2-methyl and 33% 2-ethyl are exemplified). As mentioned earlier in this R.G. Laughiin in "The Aqueous Phase Behavior of Surfactants", R.G. Laughiin, Academic Press, N.Y. (1994) p. 347 describes the observation that as the / branching moves away from the 2-alkyl position towards the center of the hydrophobic alkyl group, there is a decrease in the Krafft temperatures. See also Finger and others, "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 fk EP 342,917 A, Unilever , published on November 23, 1989 describes laundry detergents containing a surfactant system in which the main surfactant anionic is an alkyl sulfate having an adequate "broad range" of alkyl chain lengths (the experimental seems to include mixing coconut and tallow chain length surfactants).

The patent of E.U.A. 4,102,823 and GB 1, 399,966 describe other laundry compositions containing conventional alkylsulfates. British Patent 1, 299,966, Matheson et al., Published on July 2, 1975, discloses a detergent composition in which the surfactant system is comprised of a mixture of sodium tallow alkyl sulfate and nonionic surfactants. Methyl-substituted sulphates include the known "isostearyl sulfates; these are typical mixtures of isomeric sulfates having a total of 18 carbon atoms. For example, EP 401, 462 A, assigned to Henkel and published on December 12, 1990, discloses certain isostearyl alcohols and ethoxylated isostearyl alcohols and their sulfation to produce the corresponding alkyl sulfates such as sodium isostearylsulfate. See K.R. Wormuth and S. Zushma, Langmuir, Vol. 7, (1991), pp 2048-2053 (technical studies on a number of branched alkyl sulphates, especially of the "branched Guerbet" type); R. Varadaraj et al., J. Phys. Chem., Vol. 95, (1991), pp 1671-1676, (which describes the surface tensions of a variety of "linear Guerbet" and "branched-chain" surfactants Guerbet "including alkyl sulphates); Varadaj et al., J. Colloid and Interface Sci., Vol. 140, (1990), pp 31-34 (which refers to foaming data for surfactants including C12 and C13 alkyl sulphates containing 3 and 4 branches methyl, respectively); and Varadaj et al., Langmuir, Vol 6 (1990), pp 1376-1378 (which describes the micropolarity of aqueous micellar solutions of surfactants including branched alkyl sulphates). "Linear Guerbet" alcohols are available from Henkel, for example, EUTANOL G-16. The primary alkyl sulphates derived from alcohols made by Oxo reaction in oligomers of propylene or n-butylene are described in the patent of E.U.A. 5, 245,072, assigned to Mobil Corp. See also the patent of E.U.A. 5,284,989, assigned to Mobil Oil Corp. (a method for producing substantially linear hydrocarbons by oligomerizing a lower olefin at elevated temperatures with intermediate porous and constricted porous siliceous zeolite acid) and U.S. Patents. 5,026,933 and 4,870,038, both to Mobil Oil Corp. (a process for producing substantially linear hydrocarbons by oligomerizing a lower olefin at elevated temperatures with ZSM-23 siliceous acid zeolite). See also: Surfactant Science Series, Marcel Dekker, N.Y.

(Several volumes include those titled "Anionic Surfactants" and "Surfactant Biodegradation", the latter by RD Swisher, second edition, publ.87 as Vol.18, see especially pp. 20-24"Hydrophobic groups and their sources"; pp 28 -29; "Alcohols", pp 34-35; "Primary Alkyl Sulfates" and pp 35-36"Secondary Alkyl Sulfates"); and literature about "higher" alcohols or "detergents" from which alkyl sulphates are typically manufactured, including: CEH Marketing Research Report "Detergent Alcohols" by R.F. Modler et al., Chemical Economics Handbook, 1993, 609.5000-609.5002; Kirk Othmer's Encyclopedia of Chemical Technology, 4th edition, Wiley, N.Y. 1991, "Alcohols, Higher Aliphatic" in Vol. 1, pp 865-913 and references to them. (f 5 BRIEF DESCRIPTION OF THE INVENTION The present invention comprises detergent compositions, for example those which are useful for washing fabrics, dishes or cleaning hard surfaces, comprising: a) at least about 0.5%, preferably at least about 5%, most preferably at least about 10%, more preferably at least about 20%, by weight, of branched surfactant compounds in the middle region of their chain and the longer alkyl chain; and 15 b) from about 0.001% to about 10%, preferably from about 0.01% to about 5%, most preferably from about 0.1% to about 2% by weight, of a cellulose derivative. The branched surfactant compounds in the middle region of Its longer alkyl chain and chain in a) are of the formula: Ab-XB wherein: (a) Ab is a branched alkyl portion in the middle region of its hydrophobic chain of C9 to C22 (total carbon atoms in the portion), preferably from about C12 to about C18, which has: (1) a longer linear carbon chain attached to the -X-B portion on the scale from 8 to 21 carbon atoms; (2) one or more C1-C3 alkyl portions branching from its longest linear carbon chain; (3) at least one of the branched alkyl portions is directly attached to a carbon of the longest linear carbon chain at a position within the carbon scale of position 2 (counting from carbon # 1 that is attached to 10 the portion -XB-) to the position w-carbon 2, (the terminal carbon minus 2 carbons, ie, the third carbon from the end of the longest linear carbon chain); and (4) the surfactant composition has a total number of average carbon atoms in the A ^ -X portion in the above formula within the range of more than 14.5 to about 18 (preferably more than about 14.5 to about 17.5, most preferably from 15 to about 17); (b) B is a hydrophilic portion selected from sulfates, sulfonates, amine oxides, polyoxyalkylene (such as polyoxyethylene and polyoxypropylene), alkoxylated sulfates, polyhydroxy portions, esters of phosphate, glycerol sulfonates, polygluconates, polyphosphate esters, phosphonates, sulfosuccinates, sulfosuccinates, polyalkoxylated carboxylates, glucamides, taurinates, sarcosinates, glycinates, setionates, dialkanolamides, monoalkanolamides, monoalkanolamide sulphates, diglycolamides, diglycolamide sulfates, glycerol esters, ester sulfates glycerolics, glycerol ethers, glycerol ether sulfates, polyglycerol ethers, polyglycol ether sulfates, sorbitan esters, polyalkoxylated sorbitan esters, ammonium alkanesulphonates, amidopropylbetaines, alkylates, alkylated / polyhydroxyalkylated quats, alkylated quats, alkylated / polyhydroxyalkylated oxypropyl quads, imidazolines, 2- il-sucinates, sulfonated alkyl esters, and sulfonated fatty acids [it should be noted that more than one hydrophobic portion may be attached to B, for example as in (Ab-X) 2 ~ B to give dimethyl cells]; Y X is selected from -CH2- and -C (O) -.

Preferred are also the compositions in which in the formula previous portion A & does not have any quaternary carbon atoms substituted (ie, 4 carbon atoms directly attached to a carbon atom). Preferred surfactant detergent compositions herein include branched surfactant compounds in the middle region of their chain and longer alkyl chain of the formula above wherein the portion AD is a branched primary alkyl portion having the formula: ## STR3 ## H 2 C (H 2) WC H (C H 2) x H (CH '22) V v H (CH 2) z- where the total number of carbon atoms in the primary alkyl portion branched out of this formula (including branching R, R1 and R2) is 13 to 19; R, R1 and R2 are each independently selected from hydrogen and C1-C3 alkyl (preferably methyl), provided that R, R "and R2 do not they are all hydrogen and, when z is 0, at least R and R1 is not hydrogen; w is an integer from 0 to 13; x is an integer from 0 to 13; and is an integer from 0 to 13; z c e is an integer from 0 to 13; and w + x + y + z is from 7 to 13. Surfactant compositions which are also preferred herein include branched surfactant compounds in the middle region of their chain and longer alkyl chain of the above formula wherein the A3 portion is a branched primary alkyl portion having the formula selected from: or mixtures thereof; where a, b, d and e are integers, a + b is from 10 to 16, d + e is from 8 to 14 and where in addition, when a + b = 10, a is an integer from 2 to 9 and b is a whole from 1 to 8; when a + b = 11, a is an integer from 2 to 10 and b is an integer from 1 to 9; 20 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; 5 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. All percentages, ratios and proportions of this are by weight, unless otherwise indicated. All temperatures are in degrees centigrade (° C) unless otherwise specified.

All of the cited documents are incorporated herein by reference in a relevant manner.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to detergent compositions comprising a selected amount of cellulose derivative and branched surfactant compounds in the middle region of its chain, and longer alkyl chain as described herein. Other surfactants in addition to the branched surfactant in the middle region of its chain may be included, but not required as part of the detergent composition.

A. Branched surfactants in the middle region of their chain In said branched surfactant compositions in the middle region of their chain, certain branching points (for example, the location along the chain of the portions R, Rl and / or R ^ in the above formula) are preferred over other branch points along the base structure of the surfactant. The following formula illustrates the branch scale of the middle chain (ie, where the branching points occur), the branching scale in the middle region of the chain that is preferred, and the branching scale in the middle region of the chain chain that is most preferred for branched mono-methyl alkyl A * 3 portions.

CH3CH2CH2CH2CH2CH2 (CH2) 1-7CH2CH2CH2CH2CH2- jscale very preferred A A A preferred scale branching scale l- "5n the middle region of the chain It should be noted that for the mono-methyl substituted surfactants these scales exclude the two terminal carbon atoms of the chain and the carbon atom immediately adjacent to the -X-B group.

The following formula illustrates the branching scale in the middle region of the chain, the branching scale in the middle region of the chain that is preferred, and the branching scale in the middle region of the chain. which is most preferred for di-methyl-substituted alkyl AD portions useful in accordance with the present invention.

CH3CH2CH2CH2CH2CH2 (CH2)? - 6CH2CH2CH2CH2CH2- A A Very preferred scale *. preferred scale of branching scale 1 - in the middle region of the chain Preferred branched surfactant compositions useful in cleaning compositions according to the present invention are described in greater detail below. (1) Branched primary alginylsulfate surfactants in the region of their chain The surfactant detergent compositions may comprise one or more, preferably two or more surfactants of primary alkylsulfate branched in the middle region of its chain that have the formula R R 1 R? CH3CH2 (CH2) wCH (CH2)? CH (CH2) and CH (CH2) zOS? 3 M The surfactant mixtures comprise molecules having a linear primary alkyl sulfate chain base structure (ie, the longest linear carbon chain that includes the sulfated carbon atom). These base structures of the alkyl chain comprise from 12 to 19 carbon atoms; and also the molecules comprise a portion primary branched alkyl having at least a total of 14, but no more of 20, carbon atoms. In addition, the surfactant mixture has an average total number of carbon atoms for branched primary alkyl portions within the range of more than 14.5 to about 18. In this manner, the mixtures of the present invention comprise at least one primary alkylsulfate surfactant compound branched that has a longer linear carbon chain of not less than 12 carbon atoms or more than 19 carbon atoms, and the total number of carbon atoms / atoms including the branch must be at least 14, and also the total average number of carbon atoms for the branched primary alkyl chains is within of the scale of more than about 14.5 to about 18. For example, a total primary alkylsulfate surfactant of 16 total carbon atoms having 13 carbon atoms in the base structure must have 1, 2 or 3 branching units (ie , R, R1 and / or R2) whereby the total number of carbon atoms in the molecule is at least 20 16. In this example, the requirement of 16 total carbons can be satisfied in the same way having, for example , a propyl branching unit or three methyl branching units. R, R1 and R2 are each independently selected from hydrogen and C-1-C3 alkyl (preferably hydrogen or C1-C2 alkyl, most preferably hydrogen or methyl, and more preferably methyl), provided that R, R1 and R ^ Do not be all hydrogen. Also, when z is 1, at least R or R1 is not hydrogen. Although the surfactant compositions for the above formula do not include molecules in which the R, R 1 and R 2 units are all hydrogen (ie, unbranched linear primary alkyl sulphates), it should be recognized that the surfactant compositions may still comprise a certain amount. of unbranched linear primary alkyl sulphate. In addition, this unbranched linear primary alkyl sulfate surfactant may be present as a result of the process used to make the surfactant mixture having the requirement of one or more branched primary alkyl sulfate surfactants in the middle region of its chain, or for purposes of formulating detergent compositions, a certain amount of unbranched linear primary alkyl sulfate can be mixed into the final product formulation. Furthermore, it should be similarly recognized that the branched alcohol in the middle region of its unsulfated chain may comprise a certain amount of the branched surfactant compositions in the middle region of its chain. Such materials may be present as a result of the incomplete sulfation of the alcohol used to prepare the alkyl sulfate surfactant, or these alcohols may be added separately to the detergent compositions of the present invention together with a branched alkyl sulfate surfactant in the middle region of your chain. M is hydrogen or a salt-forming cation depending on the synthesis method. Examples of salt-forming cations are lithium, sodium, potassium, calcium, magnesium, and quaternary alkylamines having the formula: wherein R3, R4, R5 and 6 are independently hydrogen, C-1-C22 alkylene. C4-C22 branched alkylene, C1-C6 alkanol, alkenylene of C1-C22. 4-C22 branched alkenylene and mixtures thereof. The preferred cations are ammonium (R3, R4, R5 and R6 are identical to hydrogen), sodium, potassium, mono-, di- and trialkanolammonium, and mixtures thereof. The monoalkanolammonium compounds have R3 equal to C1-C6 alkanol, R4, R5 and R6 equal to hydrogen; the dialkanolammonium compounds they have R3 and R4 equal to C-i-Cβ alkanol, R ^ and R6 equal to hydrogen; the trialkanolammonium compounds have R3, R and R5 jgUa | to C-j-Cs alkanol, R6 equal to hydrogen. Preferred alkanolammonium salts are the mono-, di- and quaternary triammonium compounds having the formulas: H3N + CH2CH2OH, H2N + (CH2CH2OH) 2, HN + (CH2CH2OH) 3 The M that is preferred is sodium, potassium salts and C2 alkanolammonium listed above; Sodium is more preferred.

Still 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; and w + x + y + z is an integer from 8 to 14. The surfactant mixtures that are preferred to be used in the present invention have at least 0.001%, most preferably at least 5%, more preferably at least 20% by weight, of the mixture of one or more branched primary alkyl sulphates having the formula: wherein the total number of carbon atoms, including the branching, is from 15 to 18, and wherein in addition for this surfactant mixture the total average number of carbon atoms in the primary branched alkyl portions having the above formula is on the scale of more than 14.5 to about 18; R1 and R2 are each independently hydrogen or C 1 -C 3 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; as long as R1 and R ^ are not both hydrogen. More preferred are compositions having at least 5% of the mixture comprising one or more branched primary alkyl sulphates in the middle region of their chain wherein x + y equals 9 and z is at least 2. Preferably, the mixtures of surfactant comprise at least 5% of a branched primary alkyl sulfate in the middle region of its chain having R 1 and R 2 independently being hydrogen, methyl, provided that R 1 and R 2 are not both hydrogen; x + y are equal to 8, 9 or 10 and z is at least 2. Most preferably, the surfactant mixtures comprise at least 20% of a branched primary alkyl sulfate in the middle region of its chain having R1 and R2 being independently hydrogen, methyl, provided that R ^ and R ^ are not both hydrogen; x + y are equal to 8, 9 or 10 and z is at least 2. Preferred detergent compositions according to the present invention, for example a fabric washing tool, comprise from about 0.001% to about 99% of a mixture of branched primary alkyl sulfate surfactants in the middle region of its chain, said mixture comprises at least about 5% by weight of two or more branched alkyl sulphates in the middle region of its chain having the formula: 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 of 1 to 8; when a + b = 11, a is an integer from 2 to 10 and b is an integer from 1 to 9; when a + b = 12, a is an integer from 2 to 1 1 and b is an integer of 1 a.10; when a + b = 13, a is an integer from 2 to 12 and b is an integer from 1 to 1 1; 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 1 1 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 1 1; when d + e = 14, d is an integer from 2 to 13 and e is an integer from 1 to 12; wherein also for this surfactant mixture, the total average number of carbon atoms in the primary branched alkyl portions having the above formulas is within the range of more than 14.5 to about 18. In addition, the branched surfactant composition in the middle region of its chain may comprise a mixture of branched primary alkyl sulphates having the formula: R R 1 R2 III CH3CH2 (CH2) wCH (CH2)? CH (CH2) and CH (CH2) zOS03M wherein the total number of carbon atoms per molecule, including branching, is from 14 to 20, and wherein in addition to this mixture of surfactant the total average number of carbon atoms in the branched primary alkyl portions having the formula above is on the scale of more than 14.5 to about 18; R, R1 and R2 are each independently selected from hydrogen and C1-C3 alkyl; as long as R, R1 and R ^ are not all hydrogen; M is a cation soluble in water; w is an integer from 0 to 13; x is an integer from 0 to 13; and is an integer from 0 to 13; z is an integer of at least 1 and w + x + y + z is from 8 to 14; with the proviso that when R2 is a C 1 -C 3 alkyl the ratio of surfactants having z equal to 1 to surfactants having z of 2 or more is at least about 1: 1, preferably at least less about 1: 5, rr? ü and preferably at least about 1: 10 and more preferably at least about 1: 100. Also preferred are surfactant compositions wherein R2 is a C1-C3 alkyl, comprising less than about 20%, preferably less than about 10%, most preferably less than 5% and more preferably less than 1% alkyl sulfates Branched primaries having the above formula wherein z is equal to 1. The mono-methyl branched primary alkyl sulphates are selected from the group consisting of: 3-methylpentadecanolsulfate, 4-methylpentadecanolsulfate, 5-methylpentadecanolsulfate, 6-methylpentadecanolsulfate, 7-methylpentadecanolsulfate, 8-methylpentadecanolsulfate, 9-methylpentadecanolsulfate, 10-methylpentadecanolsulfate, 11 -methylpentadecanolsulfate, 12-methylpentadecanolsulfate, 13-methylpentadecanolsulfate, 3-methylhexadecanolsulfate, 4-methylhexadecanolsulfate, 5-tffc methylhexadecanolsulfate, 6-methylhexadecanolsulfate, 7-methylhexadecanolsulfate, 8-methylhexadecanolsulfate, 9 - methylhexadecanolsulfate, 10-methylhexadecanolsulfate, 11-methyl lhexadecanolsulfate, 12-methylhexadecanolsulfate, 13-methylhexadecanolsulfate, 14-methylhexadecanolsulfate and mixtures thereof. The preferred di-methyl branched alkyl sulfates which are preferred are selected from the group consisting of: 2,3-methyltetradecanolsulfate, 2,4-methyltetradecanolsulfate, 2,5-methyltetradecanolsulfate, 2,6-methyltetradecanolsulfate, 2,7-methyltetradecanolsulfate, 2 , 8-methyltetradecanolsulfate, 2,9-methyltetradecanolsulfate, 2,10- 15 methyltetradecanolsulfate, 2,11-methyltetradecanolsulfate, 2,12-methyltetradecanolsulfate, 2,3-methylpentadecanolsulfate, 2,4-methylpentadecanolsulfate, 2,5-methylpentadecanolsulfate, 2, 6- methylpentadecanolsulfate, 2,7-methylpentadecanolsulfate, 2,8-methylpentadecanolsulfate, 2,9-methylpentadecanolsulfate, 2,10- 20 methylpentadecanolsulfate, 2,11 -methylpentadecanolsulfate, 2,12- methylpentadecanolsulfate, 2,13-methylpentadecanolsulfate and mixtures of same. The following branched primary alkyl sulphates comprising 16 carbon atoms and having a branching unit are examples of preferred branched surfactants: 5-methylpentadecylsulfate having the formula: 6-methylpentadecylsulfate having the formula: 7-methylpentádecyl sulfate having the formula: 8-methylpentadecylsulfate having the formula: 9-methylpentadecylsulfate having the formula: -methylpentadecylsulfate having the formula: wherein M is preferably sodium.

The following branched primary alkyl sulphates comprising 17 carbon atoms and having two branching units are examples of preferred branched surfactants: 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. (2) Branched primary alkoxy polyoxyalipylene surfactants in the middle region of its chain Branched surfactant compositions may comprise one or more branched primary alkyl polyoxyalkylene surfactants in the middle region of their chain having the formula: R R1 R * I I CH3CH2 (CH2) ^ H (CH2) ^ CH2) and CH (CH2) z (EsPO) mOH The surfactant mixtures comprise molecules having a linear primary polyoxyalkylene chain base structure (ie, the longest linear carbon chain including the alkoxylated carbon atom). These base structures of the alkyl chain comprise from 12 to 19 carbon atoms; and in addition the molecules comprise a branched primary alkyl portion having at least a total of 14, but not more than 20, carbon atoms. In addition, the surfactant mixture has an average total number of carbon atoms for branched primary alkyl portions within the range of more than 14.5 to about 18. In this manner, the blends of the present invention comprise at least one polyoxyalkylene compound having a longer linear carbon chain of not less than 12 carbon atoms or more than 19 carbon atoms, and the total number of carbon atoms The carbon including the branching must be at least 14, and furthermore the total average number of carbon atoms for the branched primary alkyl chains is within the range of more than 14.5 to about 18. For example, a primary polyoxylakylene surfactant of 16 total carbons (in the alkyl chain) having 15 carbon atoms in the base structure must have a branching unit (either R, R1 or R2 is methyl) whereby the total number of carbon atoms in the The molecule is at least 16. R, Rl and R ^ are each independently selected from hydrogen and C 1 -C 3 alkyl (preferably hydrogen or C 2 -C 2 alkyl, most preferably hydrogen or lime, and most preferably methyl), so long as R, R1 and R2 are not all hydrogen. Also, when z is 1, at least R or Rl is not hydrogen. Although the surfactant compositions of the above formula do not include molecules in which the units R, Rl and R ^ are all hydrogen (ie linear, unbranched primary polyoxyalkylenes), it should be recognized that the surfactant compositions may still comprise adeny a certain amount of unbranched linear primary polyoxyalkylene. In addition, this unbranched linear primary polyoxyalkylene surfactant may be present as a result of the process used to make the surfactant mixture having the branched primary polyoxyalkylenes in the middle region of its chain required, or for the purposes of formulating certain detergent compositions. Amount of unbranched linear primary polyoxyalkylene can be mixed into the final product formulation. Furthermore, it should be similarly recognized that the branched alcohol in the middle region of its non-alkoxylated chain may comprise a certain amount of the polyoxyalkylene-containing compositions of the present invention. Such materials may be present as a result of the incomplete alkoxylation of the alcohol used to prepare the polyoxyalkylene surfactant, or these alcohols may be added separately to the detergent compositions of the present invention together with a branched polyoxyalkylene surfactant in the middle region of its chain. 5 Still with respect to the previous formula, w is an integer from 0 to 13; x is an integer from 0 to 13; and is an integer from 0 to 13; z is an integer of at least 1; and w + x + y + z is an integer from 8 to 14. EO / PO are alkoxy portions, preferably selected from mixed ethoxy, propoxy and ethoxy / propoxy groups, most preferably ethoxy, in Wherein m is at least about 1, preferably on the scale from about 3 to about 30, most preferably from about 5 to about 20 and more preferably from about 5 to about 15. The portion (EO / PO) m may be, or a distribution with average degree of alkoxylation (for example, ethoxylation and / or propoxylation) corresponding to m, or can be an individual specific chain with alkoxylation (for example, ethoxylation and / or P propoxylation) exactly of the number of units corresponding to m. Preferred surfactant mixtures have at least 0.001%, most preferably at least 5%, more preferably 20 at least 20% by weight, of the mixture of one or more branched primary alkylpolyoxyalkylenes having the formula: R1 R2 I I CH3CH2 (CH2)? CH (CH2) and CH (CH2) z (EO / PO) mOH wherein the total number of carbon atoms, including the branching, is from 15 to T8, and in addition for this mixture of surfactant the total average number of carbon atoms in the alkyl portions '%. branched primaries that have the above formula is on the scale of more from 14.5 to about 18; R "and R ^ are each independently hydrogen or C1-C3 alkyl, x is from 0 to 11, and is from 0 to 11, z is therefore minus 2; and x + y + z is from 9 to 13; as long as R ^ and R ^ are not both hydrogen; and EO / PO are alkoxy portions selected from mixed ethoxy, propoxy and ethoxy / propoxy groups, most preferably ethoxy, wherein m is At least about 1, preferably on the scale of about 3 to about 30, most preferably about 5 to about 20 and more preferably about 5 to about 15. Most preferred are compositions having at least 5% the mixture comprising one or more branched primary polyoxyalkylenes in the middle region of their chain in which z is at least 2. Preferably, the surfactant mixtures comprise at least 5%, preferably at least about 20%, of an alkyl polyoxyalkylene branched primary in the The middle region of its chain having R 1 and R 2 being independently hydrogen or methyl, provided that R 1 and R 2 are not both hydrogen; x + y are equal to 8, 9 or 10 and z is at least 2. Preferred detergent compositions according to the present invention, for example a fabric washing tool, comprise from about 0.001% to about 99% of a mixture of primary alkylpolyoxyalkylene surfactants branched in the middle region of their chain, said mixture comprises at least about 5% by weight of one or more branched alkylpolyoxyalkylenes in the middle region of their chain having the formula: or mixtures thereof; where a, b, d and e are integers, a + b is 10 a 16, d + e is from 8 to 14 and where in addition, when a + b '= 10, a is an integer from 2 to 9 and b is an integer from 1 to 8; when a + b = 11, a is an integer from 2 to 10 and b is an integer from 1 to 9; when a + b = 12, a is an integer from 2 to 11 and b is an integer from 1 to 10 when a + b = 13, a is an integer from 2 to 12 and b is an integer from 1 to 11 when a + b = 14, a is an integer from 2 to 13 and b is an integer from 1 to 12 when a + b = 15, a is an integer from 2 to 14 and b is an integer from 1 to 13 when a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to 14 when d + e = 8, d is an integer from 2 to 7 and e is an integer from 1 to 6; when d + e = 9, d is an integer from 2 to 8 and e is an integer from 1 to 7; when d + e = 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d + e = 11, d is an integer from 2 to 10 and e is an integer from 1 to .9; when d + e = 12, d is an integer from 2 to 11 and e is an integer from 1 to 10; when d + e = 13, d is an integer from 2 to 12 and e is an integer from 1 to 11; i when d + e = 14, d is an integer from 2 to 13 and e is an integer from 1 to 12; wherein also for this surfactant mixture, the total average number of carbon atoms in the primary branched alkyl portions having the above formulas is within the range of more than 14.5 to about 18; and EO / PO are selected alkoxy portions of mixed ethoxy, propoxy and ethoxy / propoxy groups, where m is At least about 1, preferably on the scale of about 3 to about 30, most preferably from about 5 to about 20 and more preferably from about 5 to about 15. In addition, the surfactant composition of the present The invention may comprise a mixture of branched primary alkyl polyoxyalkylenes having the formula: R R1 R2 I I I CH3CH2 (CH2) ^ CH (CH2)? CH (CH2) CH (CH2) -iEO / PO) mOH where the total number of carbon atoms per molecule, including the branch, is from 14 to 20, and where in addition for this agent mixture surfactant the total average number of carbon atoms in the branched primary alkyl portions having the above formula is in the range of more than 14.5 to about 18; R ^ and R2 are each independently selected from hydrogen and C-1-C3 alkyl; as long as R, R1 and R are not all hydrogen; w is an integer from 0 to 13; x is an integer from? f 0 to 13; and is an integer from 0 to 13; z is an integer of at least 1; and w + x + y 5 + z is from 8 to 14; EO / PO are alkoxy portions preferably selected from mixed ethoxy, propoxy and ethoxy / propoxy groups, wherein m is at least about 1, preferably in the range from about 3 to about 30, most preferably from about 5 to about 20 and more preferably about 5 to about 15; provided that when R2 is a C1-C3 alkyl the ratio of surfactants having z equal to 2 or more to the surfactants having z of 1 is at least about 1: 1, preferably at least about 1.5: 1, most preferably at least about 3: 1 and more preferably at least about 4: 1. Also preferred are surfactant compositions in which R is a C 1 -C 3 alkyl, comprising less than about 50%, preferably less than about 40%, most preferably less than about 25% and more preferably less than about 20% of branched primary alkyl polyoxyalkylene having the above formula wherein z is equal to 1. The mono-methyl branched primary alkyl ethoxylates are selected from the group consisting of: 3-methylpentadecanoletoxylate, 4-methylpentadecanolethoxylate, 5-methylpentadecanolethoxylate, 6-methylpentadecanolethoxylate, 7-metilpentadecanoletoxílato, metilpentadecanoletoxilato 8-, 9-metilpentadecanoletoxilato, 10- metilpentadecanoletoxilato 11 -metilpentadecanoletoxilato, metilpentadecanoletoxilato 12-, 13-metilpentadecanoletoxilato, metilhexadecanoletoxilato 3-, 4-metilhexadecanoletoxilato, 5-metilhexadecanoletoxilato, 6-metilhexadecanoletoxilato, 7-metilhexadecanoletoxilato, 8- methylhexadecanol ethoxylate, 9-methylhexadecanolethoxylate, 10-methylhexadecanolethoxylate, 11-methylhexadecanolethoxylate, 12-methylhexadecanolethoxylate, 13-methylhexadecanolethoxylate, 14-methylhexadecanolethoxylate and mixtures thereof, wherein the compounds are ethoxylated with an average degree of ethoxylation of from about 5 to about 15. The di-methyl branched primary alkyl ethoxylates which are preferred are selected from the group consisting of: 2,3-methyltetradecanoletoxylate, 2,4-methyltetradecanolethoxylate, 2,5-methyltetradecanolethoxylate, 2,6-methyltetradecanolethoxylate, 2,7-methyltetradecanolethoxylate, , 8-methyltetradecanoletoxylate, 2,9-methyltetradecanoletoxylate, 2,10-methyltetradecanol-ethoxylate, 2,11-methyltetradecanolethoxylate, 2,12-methyltetradecanolethoxylate, 2,3-methylpentadecanolethoxylate, 2,4-methylpentadecanolethoxylate, 2,5-methylpentadecanolethoxylate, 2 , 6-methylpentadecanoletoxilato, 2,7-methylpentadecanoletoxilato, 2,8-methylpentadecanoletoxilato, 2,9-methylpentadecanoletoxilato, 2,10-me tilpentadecanoletoxilato,. 2,11- methylpentadecanol-ethoxylate, 2,12-methylpentadecanoletoxylate, 2,13-methylpentadecanolethoxylate and mixtures thereof, wherein the The compounds are ethoxylated with an average degree of ethoxylation of about 5 to about 15. (3) Branched primary alkoxylated alkoxylated surfactant surfactants in the middle region of its chain The branched surfactant compositions may comprise one or more (preferably a mixture of two or more) primary alkoxylated alkylsulphate surfactants branched in the middle region of their chain having the formula: R R1 R2 I I I CH3CH2 (CH2) wCH (CH2)? CH (CH2) and CH (CH2) z (EO / PO) mOS03lv1 The surfactant mixtures comprise molecules that they have a linear primary alkoxylated sulfate chain base structure (i.e., the longest linear carbon chain that includes the alkoxysulfated carbon atom). These alkyl base structures comprise from 12 to 19 carbon atoms; and also the molecules comprise a portion branched primary alkyl having at least a total of 14, but not more than 20, carbon atoms. In addition, the surfactant mixture has an average total number of carbon atoms for branched primary alkyl portions within the range of more than 14.5 to about 18. In this manner, the mixtures of the present invention comprise at least one compound of alkoxylated sulfate having a longer linear ff carbon chain of not less than 12 carbon atoms or more than 19 atoms carbon, and the total number of carbon atoms including the branch must be at least 14, and in addition the total average number of carbon atoms for branched primary alkyl chains is within the range of more than 14.5 to about 18. For example, an alkoxylated alkyl sulfate surfactant The primary of 16 total carbons (in the alkyl chain) having 15 carbon atoms in the base structure must have a branching unit (either R, R 1 OR is methyl) whereby the total number of carbon atoms in the primary alkyl portion of the molecule is 16. R, R1 and R are each independently selected from Hydrogen and C-J-C3 alkyl (preferably hydrogen or C-1-C2 alkyl, most preferably hydrogen or methyl, and more preferably methyl), provided that R, R1 and R2 are not all hydrogen. Also, when z is 1, at least R or Rl is not hydrogen. Although the surfactant compositions of the present invention the above formula does not include molecules in which the R units, R1 and R are all hydrogen (i.e., unbranched linear primary alkoxylated sulfates), it should be recognized that the compositions of the present invention may still further comprise a certain amount of unbranched linear primary alkoxylated sulfate. In addition, this unbranched linear primary alkoxylated sulfate surfactant may be present as a result of the process used to make the surfactant mixture having the branched primary alkoxylated sulphates in the middle region of its chain necessary, or for the purposes of formulating compositions detergents a certain amount of unbranched linear primary alkoxylated sulfate can be mixed into the final product formulation. It should also be recognized that a certain amount of branched alkyl sulfate in the middle region of its chain may be present in the compositions. This is typically the result of the sulfation of a non-alkoxylated alcohol which remains after the incomplete alkoxylation of the branched alcohol in the middle region of its chain used to prepare the alkoxylated sulfate of the present. However, it should be recognized that the separate addition of said branched alkyl sulphates in the middle region of their chain is also contemplated by the compositions of the present invention. Furthermore, it should be similarly recognized that the branched alcohol in the middle region of its unsulfated chain (including the polyoxyalkylene alcohols) may comprise a certain amount of the alkoxylated sulfate-containing compositions of the present invention. Such materials may be present as a result of the incomplete sulfation of the alcohol (alkoxylated or non-alkoxylated) used to prepare the alkoxylated sulfate surfactant, or these alcohols may be added separately to the detergent compositions of the present invention. together with a branched alkoxylated sulfate surfactant in the region average of your chain. * 9 M is as described above in this. 5 More with respect to the previous formula, w is an integer from 0 to 13; x is an integer from 0 to 13; and is an integer from 0 to 13; z is an integer of at least 1; and w + x + y + z is an integer from 8 to 14. EO / PO are alkoxy portions, preferably selected from mixed ethoxy, propoxy and ethoxy / propoxy groups, wherein m is at least about 0.01, preferably on the scale of about 0.1 to about 30, most preferably from about 0.5 to about 10 and more preferably from about 1 to about 5. The portion (EO / PO) m may be, or a distribution with average degree of alkoxylation (eg, ethoxylation and / or propoxylation) corresponding to m, or can be an individual specific chain with alkoxylation (eg, ethoxylation and / or propoxylation) of exactly the number of units corresponding to m.

Preferred surfactant mixtures have at least 0.001%, most preferably at least 5%, more preferably 20 at least 20% by weight of the mixture, of one or more alkyl sulfates Branched primary alkoxylates having the formula: R1 R2 I I CH3CH2 (CH2)? CH (CH2) and CH (CH2) z (EO / PO) mOS03M wherein the total number of carbon atoms, including branching, is from 15 to 18, and in addition for this mixture of surfactant the total average number of carbon atoms in the branched primary alkyl portions having the above formula is in the range of more than 14.5 to about 18; R1 and R2 are each independently hydrogen or C 1 -C 3 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; as long as R1 and R are not both hydrogen; and EO / PO are alkoxy portions selected from mixed ethoxy, propoxy and ethoxy / propoxy groups, wherein m is at least about 0.01, preferably on the scale of about 0.1 to about 30, most preferably about 0.5 to about 10 and more preferably from about 1 to about 5. Further preferred are compositions having at least 5% of the mixture comprising one or more branched primary alkoxylated sulfates in the middle region of their chain wherein z is at least 2. In Preferably, the surfactant mixtures comprise at least 5%, preferably at least about 20%, of a branched primary alkoxylated alkylsulfate in the middle region of its chain having R ^ and R independently being hydrogen or methyl, provided that when R1 and R2 are not both hydrogen; x + y are equal to 8, 9 or 10 and z is at least 2. Preferred detergent compositions according to the present invention, for example a fabric washing tool, comprise from about 0.001% to about 98.998% of a mixture of primary branched alkoxylated alkylsulphate surfactants in the% middle region of its chain, said mixture comprises at least about 5% by weight of one or more branched alkoxylated alkyl sulphates in the middle region of their chain having the formula: or mixtures thereof; where M represents one or more cations, a, b, d and e are integers, a + b is from 10 to 16, d + e is from 8 to 14 and where also when a + b '= 10, a is an integer from 2 to 9 and b is an integer from 1 to 8; 15 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; ? k 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; 20 when a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to 14; when d + e = 8, d is an integer from 2 to 7 and e is an integer from 1 to 6; when d + e = 9, d is an integer from 2 to 8 and e is an integer from 1 to 7; when d + e = 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d + e = 11, d is an integer from 2 to 10 and e is an integer from 1 to 9; when d + e = 12, d is an integer from 2 to 11 and e is an integer from 1 to 10; when d + e = 13, d is an integer from 2 to 12 and e is an integer from 1 to 11; when d + e = 14, d is an integer from 2 to 13 and e is an integer from 1 to 12; and wherein also for this surfactant mixture, the total average number of carbon atoms in the primary branched alkyl portions having the above formulas is within the range of more than 14.5 to about 18; and EO / PO are alkoxy portions selected from mixed ethoxy, propoxy and ethoxy / propoxy groups, wherein m is at least about 0.01, preferably in the range from about 0.1 to about 30, most preferably from about 0.5 to about 10 and more preferably from about 1 to about 5. In addition, the surfactant composition may comprise a mixture of branched primary alkoxylated alkyl sulfates having the formula: R R1 R? CH3CH2 (CH2) wCH (CH2)? CH (CH2) and CH (CH2) z (EO / PO) mOS03 M wherein the total number of carbon atoms per molecule, including branching, is from 14 to 20, and wherein in addition to this mixture of surfactant the total average number of carbon atoms in the primary branched alkyl portions having the formula above is on the scale of more than 14.5 to about 18; R, R ^ and R2 are each independently selected from hydrogen and C 1 -C 3 alkyl; as long as R, R1 and R2 are not all hydrogen; M is a cation soluble in water; w is an integer from 0 to 13; x is an integer from 0 to 13; and is an integer from 0 to 13; z is an integer of at least 1; w + x + y + z is from 8 to 14; EO / PO are alkoxy portions preferably selected from mixed ethoxy, propoxy and ethoxy / propoxy groups, wherein m is at least about 0.01, preferably on the scale from about 0.1 to about 30, most preferably from about 0.5 to about 10 and more preferably from about 1 to about 5; provided that when R2 is an alkyl / of CJ-C3 the ratio of surfactants having z equal to Zo plus to surfactants having z of 1 is at least about 1: 1, preferably at least about 1.5: 1, most preferably at least about 3: 1 and more preferably at least about 4: 1. Also preferred are surfactant compositions wherein R2 is a C1-C3 alkyl, comprising less than about 50%, preferably less than about 40%, most preferably less than about 25% and more preferably less than about 20% , of branched primary alkoxylated alkylsulfate having the above formula wherein z is equal to 1. The mono-methyl branched primary ethoxylated alkyl sulphates are selected from the group consisting of: 3-methylpentadecanoletoylated sulfate, 4-methylpentadecanol-ethoxylated sulfate, sulfate 5- methylpentadecanoletoylated sulfate, 6-methylpentadecanoletoylated sulfate, 7-methylpentadecanol-ethoxylated sulfate, 8-methylpentadecanoletoylated sulfate, 9-methylpentadecanoletoylated sulfate, 10-methylpentadecanol-ethoxylated sulfate, 11-methylpentadecanolethoxylated sulfate, 12-methylpentadechanoxylated sulfate, 13-methylpentadecanol-ethoxylated sulfate, sulfate 3 -methylhexadecanoletoylated, 4-methylhexadecanoletoxi sulfate side, 5-methylhexadecanoletoxilado, 6-methylhexadecanoletoxilado sulfate, 7-metilhexadecanol-ethoxylated sulfate, 8-methylhexadecanoletoxilado sulfate 9-methylhexadecanoletoxilado sulfate, 10-methylhexadecanol-ethoxylated sulfate, 11-methylhexadecanoletoxilado sulfate, 12-methylhexadecanoletoxilado sulfate, 13-methylhexadecanol-ethoxylated sulphate , 14-methylhexadecanoletoxylated sulfate and mixtures thereof, wherein the compounds are ethoxylated with an average degree of ethoxylation of from about 0.1 to about 10. The preferred di-methyl branched primary alkyl ethoxylates are selected from the group consisting of: sulfate 2, 3-methyltetradecanoletoylated, 2,4-methyltetradecanoletoylated sulfate, 2,5-methyltetradecanol-ethoxylated sulfate, 2,6-methyltetradecanoletoylated sulfate, 2,7-methyltetradecanolethoxylated sulfate, 2,8-methyltetradecanol-ethoxylated sulfate, 2,9-methyltetradecanolethoxylated sulfate , 2,10-methyltetradecanoletoxilado sulfato, 2,11-metiltetradecanoletoxilado sulfate, 2,12-metiltetradecanol-ethoxylated sulfate, 2,3-methylpentadecanoletoxila sulfate, 2,4-methylpentadecanoletoxila sulfate, 2,5-methylpentadecanol-ethoxylated sulfate, sulfate 2, 6-methylpentadecanoxylethoxylated, 2,7-methylpentadecan-letoxylated sulfate, 2,8-methylpentadecanol-ethoxylated sulfate, 2,9-methylpentadecanooxylated sulfate, 2,10-methylpentadecanolatexylated sulfate, sulfate ^ f 2,11 -methylpentadecanolethoxylated, sulphate 2,12- methylpentadecanol-ethoxylate, ,13-methylpentadecanooxylated sulfate and mixtures thereof, wherein the compounds are ethoxylated with an average degree of ethoxylation of about 0.1 to about 10.

Preparation of branched surfactants in the middle region of their chain The following reaction scheme presents a general approach to the preparation of the branched primary alcohol in the middle region of its chain useful for alkoxylation and / or sulfation to prepare the surfactants of primary branched alkyl in the middle region of its chain.

OR II OH OAc Mg CI (CH2) 3-C-CH3 H30 | AcjO 1 R X ^ - R g X - 1? - - - R-C- (CH2) 3CI R-C- (CH2) 3CI CH, CH3 ? - HO Ac '' H2) 3 CI An alkyl halide is converted into a reactant of Grignard and this one is reacted with a halocetone. After conventional acid hydrolysis, acetylation and thermal removal of the acetic acid, an intermediate olefin is produced (not shown in the scheme) which is hydrogenated immediately using any convenient hydrogenation catalyst such as Pd / C. This route is favorable over others because the branch, in this illustration a 5-methyl branch, is introduced at the beginning of the reaction sequence. The formylation of the alkyl halide resulting from the first hydrogenation step produces alcohol, as shown in the scheme.

This can be alkoxylated using any convenient sulfation agent, for example, chlorosulfonic acid, S03 / air, or oil, to produce the final branched primary alkyl surfactant. There is flexibility for extend the branching an additional carbon beyond that achieved by a single form. For example, said extension can be achieved by reaction with ethylene oxide. See "Grignard Reactions of Nonmetallic Substances ", M.S. Kharasch and O. Reinmuth, 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 and others, Vol. 15 (1950), pp. 135-138, which are incorporated herein by reference.

In variations to the above procedure, alternative halogenates or Grignard reagents can be used. Halogenation with PBr3 of the alcohol that comes from formylation or ethoxylation can be used to achieve an iterative chain extension. The alkoxylated primary alkyl sulphates branched in the middle region of their chain which are preferred (as well as the polyoxyalkylenes and alkyl sulfates, by only choosing alkoxylating or sulfating the produced intermediate alcohol) can also be easily prepared as follows: Br- "> 3P + Br- ^ - \ ^ ~ ^ ~, H CH3CH, (PH) 3P 2NaH Reflux 0 uHp DMSO THF '1) H30 * 2) CHROMATOGRAPHY O-Na * ^ ^ - - ^ - ^ - - ^ - ^ - ^ - - ^ ^ (EO / PO t? OSO, Na «- 3) Pt H20 ^" ^ ^ - ^ ^ - ^ ^ - ^ ^^ ^ "^ ^" ^ 4) AICOXLACDNSULFATACION A conventional bromoalcohol is reacted with triphenylphosphine followed by sodium hydride, suitably dimethyl sulfoxide / tetrahydrofuran, to form a Wittig adduct. The Wittig adduct is reacted with an alphamethyl ketone, forming an internally saturated alcohol-methyl branched alcohol. Hydrogenation followed by alkoxylation and / or sulfation produces the branched alkyl primary surfactant in the middle region of its chain. Although Wittig's approach does not allow the practitioner to extend the hydrocarbon chain, as in the Grignard sequence, Wittig's approach typically produces higher yields. See Agriculture! and Biological Chemistry, M. Horiike et al., vol. 42 (1978), pp 1963-1965, included herein by way of reference. Any alternative synthetic procedure can be used to Prepare the branched chain primary alkyl surfactants.

In addition, branched chain primary alkyl surfactants can be synthesized or formulated in the presence of conventional homologs, for example, any of those that can be formed in an industrial process and that produce 2-alkyl branching as a result of hydroformylation . Agent mixtures The branched surfactant in the middle region of its chain of the present invention is routinely added to other known commercial alkyl surfactants and contained in the final laundry product formulation. Certain preferred embodiments of agent mixtures Surfactant, especially those derived from fossil fuel sources including commercial processes, comprise at least 1 branched primary alkyl surfactant in the middle region of its chain, preferably at least 2, most preferably at least 5, more preferably at least 8. Particularly suitable for the preparation of certain surfactant mixtures of the present invention are "oxo" reactions, in which a branched chain olefin is subjected to isomerization and catalytic hydroformylation prior to alkoxylation and / or sulfation. Preferred methods that result in said blends use fossil fuels as the source of supply of the starting material. The procedures that are preferred use the reaction 9 v SEE * Oxo in linear olefins (alpha or internal) with a limited amount of branch. Suitable olefins can be manufactured by the dimerization of linear internal olefins or olefins, by means of the controlled oligomerization of linear olefins of low molecular weight, by the skeletal rearrangement of detergent-grade olefins, by dehydrogenation / skeletal rearrangement of paraffins. detergent, or by the Fischer-Tropsch reaction. These reactions will generally be controlled to: 1) give a large proportion of olefins in the desired detergent grade (while permitting the addition of a carbon atom in the subsequent Oxo reaction); 15 2) produce a limited number of branches, preferably of medium chain; 3) producing branches of C-1-C3, most preferably ethyl, more preferably methyl; 4) limit or eliminate dialkyl gem branch, that is, to avoid the formation of quaternary carbon atoms. Suitable olefins can be subjected to the Oxo reaction to give primary alcohols either directly or indirectly through the corresponding aldehydes. When an internal olefin is used, an Oxo catalyst is normally used which is capable of the pre-preomerization of internal olefins mainly to alpha olefins. Although an internal isomerization to catalyzed alpha can be carried out separately (ie, not Oxo), 9 this is optional. On the other hand, if the step of forming the olefin gives as As a direct result of an alpha olefin (for example, with Fischer-Tropsch olefins of detergent-grade pressure), then the use of an Oxo non-isomerization catalyst is not only possible, but is preferred. The process described hereinabove gives the 5-methyl-hexadecyl surfactants in a higher yield than the less preferred 2,4-dimethylpentadecyl surfactants. This mixture is any time that each product comprises a total of 17 carbon atoms with linear alkyl chains having at least 13 carbon atoms. For the preparation of branched surfactants in the middle region of its chain of the present wherein X is C (O) -, the branched carboxylic acids in the middle region of its chain of fc batch can be obtained from the corresponding alcohols described hereinabove by oxidation of Jones, K. Bowden, I.M.

Heilbron, E.R.H. Jones and B.C.I. Weedon, J. Chem. Soc. 1946, 39 and H.O.

House, Modern Synthetic Reactions (W.A. Benjamin, California, 2nd edition, pp. 263-264). This is a chromic acid oxidation of the alcohol to the carboxylic acid in acidic media such as aqueous sulfuric acid. Acetone can be used to solubilize the alcohol and the carboxylic acid. The reaction is commonly rapid at room temperature. The following examples provide methods for synthesizing various compounds useful in the branched surfactants in the middle region of their chain.

EXAMPLE I Preparation of 7-methylhexadecyl ethoxylated sodium (E2) and sulfate Synthesis of (6-hydroxyhexyl) triphenylphosphonium bromide To a 5L 3-neck round bottom flask equipped with nitrogen inlet, condenser, thermometer, magnetic stirring and nitrogen outlet is added 6-bromo-1-hexanol ( 500 g, 2.76 moles), triphenylphosphine (768 g, 2.9 moles) 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 flask. The product is recrystallized from 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 gives 1140 g of the desired product as white crystals.

Synthesis of 7-methylhexadecen-1-ol To a 3-neck round bottom flask of 5L dried and equipped with magnetic stirring, nitrogen inlet, dropping funnel, thermometer and nitrogen outlet is added 70.2 g of sodium hydride 60% (1.76 moles) in mineral oil. The mineral oil is removed by washing with hexanes. Anhydrous dimethyl sulfoxide (500 ml) is added to the flask and the mixture is heated to 70 ° C until the evolution of hydrogen is stopped. The reaction mixture is cooled to room temperature followed by the addition of 1 L of aqueous tetrahydrofuran. Bromide of (6-hydroxyethyl) -triphenylphosphonium (443.4 g, 1 mol) is mixed in suspension with warm anhydrous dimethyl sulfoxide (50 ° C, 500 ml) and added slowly to the reaction mixture through the funnel. fall, keeping it at the same time at 25-30 ° C. The mixture is stirred for 30 minutes at room temperature, at which time 2-undecanone (187 g, 1.1 moles) is slowly added through a dropping funnel. The reaction is slightly exothermic and cooling is required to maintain 25-30 ° C. The mixture is stirred for 18 hours and then poured into a 5L flask 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 (500 ml) and the organic phase is separated by combining it with the oil phase of the washing with water. The organic mixture is then extracted with water 3 times (500 ml each) followed by vacuum distillation to obtain the oily clear product (132 g) at 140 ° C and 1 mm Hg.

V Hydro-induction of 7-methylhexadecen-1-ol 5 On the cover of a 3L autoclave are added 7-methylhexadecen-1-ol (130 g, 0.508 mol), methanol (300 ml) and platinum on carbon (10% by weight, 35 g). The mixture is hydrogenated at a low 180 ° C. 84.36 kg / cm nanometer of hydrogen for 13 hours, cooled and filtered under vacuum through Celite 545 with washing of Celite 545, suitably with methylene chloride. If required, filtration can be repeated to remove traces of Pt catalyst, and magnesium sulfate can be used to dry the product. The product solution is concentrated on a rotary evaporator to obtain a clear oil (124 g).

Alkoxylation of 7-methylhexadecanol To a 1 L 3-neck round-bottomed flask, dried and equipped with nitrogen inlet, magnetic stirring and a Y-shaped tube equipped with a thermometer and gas outlet, the alcohol is added. previous step For the purposes of removing the remaining amounts of moisture, the alcohol is sprayed with nitrogen for about 30 minutes at 80-100 ° C. Continuing with a nitrogen spray, sodium metal is added as the catalyst and left to melt with stirring at 120-140 ° C. With vigorous stirring, ethylene oxide gas is added in 140 minutes while maintaining the reaction temperature at 120-140 ° C. After the correct weight (equal to two equivalents of ethylene oxide) has been added, the nitrogen is sprayed through the apparatus for 20-30 minutes while the sample is allowed to cool. The 7-5 methylhexadecyl ethoxylate (average of 2 ethoxylates per molecule) is then collected.

Sulfation of 7-methylhexadecyl ethoxylate (E2) To a 3-neck round bottom flask of 1 L dried and equipped with magnetic stirring, nitrogen inlet, dropping funnel, thermometer and nitrogen outlet are added chloroform and 7- methylhexadecyl ethoxylate (E2) from the previous step. Chlorosulfonic acid is slowly added to the stirred mixture while maintaining a temperature of -30 ° C with an ice bath. Once the evolution of HCl has stopped, sodium methoxide (25% in methanol) is added slowly while maintains the temperature at 25-30 ° C until an aliquot at a concentration of 5% in water maintains a pH of 10.5. Hot ethanol (55 ° C) is added to the mixture and it is filtered under vacuum immediately. The filtrate is concentrated to a suspension on a rotary evaporator, cooled and then poured into ethyl ether. The mixture is cooled to 5 ° C and vacuum filtered to provide the sodium salt of desired ethoxylated 7-methylhexadecyl sulfate (average of 2 ethoxylates per molecule).

EXAMPLE II Synthesis of 7-methylpentadecyl ethoxylated sodium (E5) and sulfate rf Synthesis of (6-hydroxyhexyl) triphenylphosphono bromide 5 To a 5-L 3-neck round bottom flask equipped with nitrogen inlet, condenser, thermometer, magnetic stirring and nitrogen outlet are added 6- bromo-1-hexanol (500 g, 2.76 moles), triphenylphosphine (768 g, 2.9 moles) 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 flask. The product is recrystallized from anhydrous ethyl ether (1.5L) at 10 ° C. Vacuum 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. 15 Synthesis of 7-methylpentadecen-1-ol fe To a 3-neck round bottom flask of 5L dried and equipped with magnetic stirring, nitrogen inlet, dropping funnel, thermometer and nitrogen outlet is added 80 g of hydride. sodium at 20 60% (2.0 moles) in mineral oil. The mineral oil is removed by washing with hexanes. Anhydrous dimethyl sulfoxide (500 ml) is added to the flask and the mixture is heated to 70 ° C until the evolution of hydrogen is stopped. The reaction mixture is cooled to room temperature followed by the addition of 1 L of aqueous tetrahydrofuran. Bromide of (6-hydroxyethyl) triphenylphosphono (443.4 g, 1 mol) is mixed in suspension with warm anhydrous dimethyl sulfoxide (50 ° C, 500 ml) and slowly added to the V reaction mixture through the funnel of fall, keeping it at the same time at 25-30 ° C. The mixture is stirred for 30 minutes at room temperature, at which time 2-undecanone (187 g, 1.1 moles) is slowly added through a dropping funnel. The reaction is slightly exothermic and cooling is required to maintain 25-30 ° C. The mixture is stirred for 18 hours and then poured into a separatory funnel contains 600 ml of purified water and 300 ml of hexanes. After shaking the oil phase (upper), it is left to separate and the water phase is removed. The extractions of the oil phase are continued using water until both phases are clear. The organic phase is collected, vacuum distilled and purified by liquid chromatography (90:10 hexanes: ethyl acetate, silica gel stationary phase) to obtain an oily clear product (119.1 g).

Hydrogenation of 7-methylpentadecen-1-ol In the cover of a 3L autoclave (Autoclave 20 Engineers), 7-methylpentadecen-1-ol (122 g, 0.508 mol), methanol (300 ml) and platinum on carbon are added. (10% by weight, 40 g). The mixture is hydrogenated at 180 ° C under 84.36 kg / cm 2 nanometer 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 due to the platinum catalyst whereby the filtration process is repeated with concentration on a rotary evaporator; the dilution is carried out with methylene chloride (500 ml) and magnesium sulfate is added to dry the product. Filter through vacuum through Celite 545 and concentrate the filtrate on a rotary evaporator to obtain a clear oil (119 g).

Alkoxylation of 7-methylpentadecanol 10 To a 3-neck round bottom flask of 1 L dried and equipped with nitrogen inlet, magnetic stirrer and a Y-tube equipped with a thermometer and a gas outlet is added the alcohol from the preceding step . For the purposes of removing the remaining amounts of moisture, the alcohol is sprayed with nitrogen for approximately 30 minutes. minutes at 80-100 ° C. Continuing with a nitrogen spray, sodium metal is added as the catalyst and left to melt with stirring at 120-140 ° C. With vigorous stirring, ethylene oxide gas is added in 140 minutes while maintaining the reaction temperature at 120-140 ° C. After the correct weight (equal to five equivalents of oxide of ethylene) has been added, nitrogen is sprayed through the apparatus for 20-30 minutes while the sample is allowed to cool. The 7-methylpentadecyl ethoxylate (average of 5 ethoxylates per molecule) is then collected.

Sulfation of 7-methylpentadecyl ethoxylate (E5) To a 3-neck round bottom flask of 1 L dried and equipped with magnetic stirring, nitrogen inlet, dropping funnel, < < * thermometer and nitrogen outlet are added chloroform and 7-5 methylpentadecyl ethoxylate (E5) from the previous step. Chlorosulfonic acid is slowly added to the stirred mixture while maintaining a temperature of 25-30 ° C with an ice bath. Once the evolution of HCl has stopped, sodium methoxide (25% in methanol) is slowly added while maintaining the temperature at 25-30 ° C until an aliquot at a concentration of 5% in water maintain a pH of 10.5. To the mixture is added methanol and 1-butanol. The organic salt precipitate is filtered under vacuum and the methanol is removed from the filtrate on a rotary evaporator. It is cooled to room temperature, ethyl ether is added and left to stand for 1 hour. The precipitate is collected under vacuum and filtered to provide the sodium salt of desired ethoxylated 7-methylpentadecyl sulfate (average of 5 ethoxylates per molecule).

EXAMPLE III Synthesis of ethoxylated 7-methylheptadecyl sodium (E1.5) and sulfate Synthesis of (6-hydroxyalkyl) triphenyl phosphide bromide To a 5-L 3-neck round bottom flask equipped with an inlet for nitrogen, condenser, thermometer, magnetic stirring and nitrogen outlet are added 6-bromo-1-hexanol (500 g, 2.76 moles), triphenylphosphine (768 g, 2.9 moles) and acetonitrile (1800 ml) under nitrogen. The reaction mixture is heated to reflux for 72 hours. The mixture of «« * Reaction is cooled to room temperature and transferred to a 5L flask.

The product is recrystallized from anhydrous ethyl ether (1.5L) at 10 ° C. Vacuum 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-methylheptadecen-1-ol To a 3-neck round bottom flask of 5L dried and equipped with magnetic stirring, nitrogen inlet, dropping funnel, thermometer and nitrogen outlet is added 80 g of sodium hydride. to 60% (2.0 molasses) in mineral oil. The mineral oil is removed by washing with hexanes. Anhydrous dimethyl sulfoxide (500 ml) is added to the flask and the mixture is heated to 70 ° C until the evolution of hydrogen is stopped. The reaction mixture is cooled to room temperature followed by the addition of 1L of aqueous tetrahydrofuran. Bromide of (6-hydroxyethyl) triphenylphosphonium (443.4 g, 1 mol) is mixed in suspension with sulfoxide of warm anhydrous dimethyl (50 ° C, 500 ml) and added slowly to the reaction mixture through the dropping funnel, keeping it at the same time at 25-30 ° C. The mixture is stirred for 30 minutes at room temperature, at which time 2-undecanone (184.3 g, 1.1 moles) is slowly added through a dropping funnel. The reaction is slightly exothermic and cooling is required to maintain 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 shaking the oil phase (upper), it is allowed to separate and the water phase is removed, which is cloudy. 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 (mobile phase-hexanes, stationary phase-silica gel) to obtain an oily and clear product (116 g). The NMRM of the final product (in deuterium oxide) indicates a triplet of CH2-OSO3"at the resonance of 3.8 ppm, multiple band of CH2- CH2-OSO3"at the resonance of 1.5 ppm, CH2 of the alkyl chain at the resonance of 0.9-1.3 ppm and a branch point of CH-CH3 overlapping the I methyl group of the terminal of R-CJH2CH.3 at the resonance of 0.8 ppm.

Hydrogenation of 7-methylheptadecen-1-ol On the cover of a 3L autoclave (Autoclave Engineers), 7-methylpentadecen-1-ol (122 g, 0.508 mol), methanol (300 ml) and platinum on carbon ( 10% by weight, 40 g). The mixture is hydrogenated at 180 ° C under 84.36 kg / cm 2 nanometer of hydrogen for 13 hours, cooled and filtered under vacuum through Celite 545 with washing of Celite 545, with methylene chloride. Filter through vacuum through Celite 545 and concentrate the filtrate on a rotary evaporator to obtain a clear oil (108 g). • f Alkoxylation of 7-methylheptadecanol 5 To a 3-liter 3-neck round bottom flask, dried and equipped with nitrogen inlet, magnetic stirrer and a Y-tube equipped with a thermometer and a gas outlet, the alcohol is added. previous step For the purposes of removing the remaining amounts of moisture, the alcohol is sprayed with nitrogen for approximately 30 minutes. minutes at 80-100 ° C. Continuing with a nitrogen spray, sodium metal is added as the catalyst and left to melt with stirring at 120-140 ° C. With vigorous stirring, ethylene oxide gas is added in 140 minutes while maintaining the reaction temperature at 120-140 ° C. After the correct weight (equal to 1.5 equivalents of oxide of ethylene) has been added, the nitrogen is sprayed through the apparatus during -30 minutes while the sample is allowed to cool. The 7-fe methylheptadecyl ethoxylate (average of 5 ethoxylates per molecule) is then collected.

Sulfation of 7-methylheptadecyl ethoxylate (E1.5) 20 To a 3 L round neck flask dried and equipped with magnetic stirring, nitrogen inlet, dropping funnel, thermometer and nitrogen outlet are added chloroform and 7-methylheptadecyl ethoxylate (E1.5) from the previous step. Chlorosulfonic acid is slowly added to the stirred mixture while maintaining a temperature of -30 ° C with an ice bath. Once the evolution of HCl is slowly added sodium methoxide (25% in methanol) while ^ Holds the temperature at 25-30 ° C until an aliquot at a concentration of 5% in water maintain a pH of 10.5. Hot methanol (45 ° C) is added to the mixture to dissolve the branched sulphate followed immediately by vacuum filtration to remove the organic salt precipitate and repeated a second time. The filtrate is then cooled to 5 ° C, at which point ethyl ether is added and left to stand for 1 hour. The precipitate is collected by vacuum filtration to provide the sodium sulfate salt of Desired 7-methylheptadecyl ethoxylate (average of 1.5 ethoxylates per molecule).

EXAMPLE IV 15 The following alcohol samples from experimental tests at Shell Research were ethoxylated (average ethoxylation 2.5) and then sulphated by the following procedure.

Results of 13 C-NMR for branched alcohols prepared To a 250 ml 3-necked round bottom flask, dried and equipped with nitrogen inlet, magnetic stirrer and a Y-tube equipped with a thermometer and a gas outlet, the alcohol is added.

C16 (48.4 g, 0.2 moles) above. For the purposes of removing the remaining amounts of moisture, the alcohol is sprayed with nitrogen for approximately 30 minutes at 80-100 ° C. Continuing with a nitrogen spray, sodium metal (0.23 g, 0.01 mole) is added as the catalyst and left to melt with stirring at 120-140 ° C. With vigorous stirring, ethylene oxide gas (22 g, 0.5 mol) is added in 140 minutes while maintaining the reaction temperature at 120-140 ° C. After the correct weight (average of 2.5 ethoxylates per molecule) of ethylene oxide has been added, the nitrogen is sprayed through the apparatus for 20-30 minutes while the sample is allowed to cool. The golden liquid product (0.196 moles) is bottled under nitrogen. The sulfation of this C16 ethoxylate utilizes the following procedure. To a 500 ml 3-necked round bottom flask, dried and equipped with a nitrogen inlet, drop funnel, magnetic stirrer and a Y-tube equipped with a thermometer and a gas outlet are added the C16 ethoxylate from the previous step (63.4 g, 0.18 mol) and diethyl ether (75 ml). Chlorosulfonic acid (22.1 g, 0.19 mol) is slowly added to the stirred mixture while maintaining a reaction temperature of 5-15 ° C with an ice and water bath. After the chlorosulfonic acid has been added, a slow spray of nitrogen and a vacuum (254-382 mm Hg) begin to remove HCl. In the same way, the reaction is heated to 30-40 ° C with the addition of a warm water bath. After approximately 45 minutes the vacuum is increased to 635-762 mm Hg and maintained for an additional 45 minutes. The acidic reaction mixture is slowly poured into a vigorously stirred flask of 25% strength sodium methoxide (43.2 g, 0.2 mol) and methanol (200 ml) which is cooled in an ice-water bath. After confirming a pH > 12, the solution is allowed to stir approximately 15 minutes and is then poured into a glass dish. HE allows most of the solvent to evaporate overnight in the smoke cover. The next morning the plate is transferred to a vacuum drying oven. The sample is allowed to dry all day and overnight at 40-60 ° C with a vacuum of 635-762 mm Hg. The sodium salt of ethoxylated C16 sulfate (E2.5) is obtained as a sticky yellow solid (80.9 g, 93% active).

EXAMPLE V Preparation of sodium 7-methylhexadecyl sulfate Sulfation of 7-methylhexadecanol To a 3-neck round bottom flask of 1 L dried and equipped with magnetic stirring, nitrogen inlet, dropping funnel, thermometer and nitrogen outlet are added chloroform (300 ml) and 7-methylhexadecanol ( 124 g, 0.484 mol), prepared as intermediates in Example I. Chlorosulfonic acid (60 g, 0.509 mol) is slowly added to the stirred mixture while maintaining a temperature of 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 a concentration of 5% in water maintain a pH of 10.5. Hot ethanol (55 ° C, 2L) is added to the mixture. The mixture is filtered under vacuum immediately. The filtrate is concentrated to a suspension on a rotary evaporator, cooled and then drained in 2L of ethyl ether. The mixture is cooled to 5 ° C, at which point crystallization occurs, and filtered under vacuum. The crystals are dried in a vacuum oven at 50 ° C for 3 hours to obtain a white solid (136 g, 92% active by titration of cat SO 3).

EXAMPLE VI Synthesis of sodium 7-methylpentadecyl sulfate Sulfation of 7-methylpentadecanol To a 3-neck round bottom flask of 1 L dried and equipped with magnetic stirring, nitrogen inlet, dropping funnel, thermometer and nitrogen outlet are added chloroform (300 ml) and 7-methylpentadecanol ( 119 g, 0.496 moles), prepared as intermediates in Example II. Chlorosulfonic acid (61.3 g, 0.52 mol) is slowly added to the stirred mixture while maintaining a temperature of 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 a concentration of 5% in water maintain a pH of 10.5. To the mixture is added methanol (1 L) and 300 ml of 1-butanol. The inorganic salt precipitate is filtered under vacuum and the methanol is removed from the filtrate on a rotary evaporator. It is cooled to room temperature, 1 L of ethyl ether is added and it is 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 (82 g, 90% active by titration of cat SO3).

EXAMPLE VII Synthesis of 7-methylheptadecylsulphate sodium Sulfation of 7-methylheptadecanol To a 3-neck round bottom flask of 1L dried and equipped with magnetic stirring, nitrogen inlet, dropping funnel, thermometer and nitrogen outlet are added chloroform (300 ml) and 7-methylheptadecanol (102 g, 0.378 moles), prepared as intermediates in Example III. Chlorosulfonic acid (46.7 g, 0.40 mol) is slowly added to the stirred mixture while maintaining a temperature of 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 a concentration of 5% in water maintain a pH of 10.5. Hot methanol (45 ° C, 1 L) is added to the mixture to dissolve the branched sulfate followed immediately by vacuum filtration to remove the organic salt precipitate and repeated a second time. The filtrate is then cooled to 5 ° C, at which time 1 L of ethyl 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 (89 g, 88% active by cat. SO 3 concentration). The RMNH of the final product (in deuterium oxide) indicates a triplet of CH2-OSO3"at the resonance of 3.8 ppm, multiple band of CH2-CH2-OSO3- at the resonance of 1.5 ppm, CjH_2 of the alkyl chain at the resonance of 0.9-1.3 ppm and a branch point of CH-CH3 overlapping the methyl group of the terminal of R- CH.2CH3 at the resonance of 0.8 ppm. The mass spectrometry data shows a molecular peak with a mass of 349.1 which corresponds to the 7-methyleneheptadecyl sulfate. The methyl branch in position 7 is also shown due to the loss of 29 mass units in that position. The following two analytical methods for characterizing the branching in the branched surfactant compositions in the middle region of its chain are useful: 1) Separation and identification of components in fatty alcohols (before alkoxylation or after hydrolysis of alcohol sulphate) for analytical purposes). The position and length of the branching found in the fatty alcohol precursor materials is determined by GC / MS techniques [see: D.J. Harvey, Biomed. Environ. Mass Spectrom. (1989). 18 (9), 719-23; DJ. 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 alkoxysulfate components separated by MS / MS. The position and length of the branching is also determinable by ion spray techniques EM / EM or FAB-EM / EM in previously isolated fatty alcohol sulfate components.

The average total carbon atoms of the branched primary alkyl surfactants herein can be calculated from the hydroxyl value of the fatty alcohol precursor mixture or from the hydroxyl value of the alcohols recovered by extraction after the hydrolysis of the alcohol sulfate mixture according to common procedures, such as those mentioned in "Bailey's Industrial Oil and Fat Products", Volume 2, fourth edition, edited by Daniel Swern, pp 440-441.

B. Cellulose Derivative Detergent compositions comprise from about 0.001% to about 10%, preferably from about 0.01% to about 5%, most preferably from about 0.1% to about 2% by weight, of a cellulose derivative. Preferred cellulose derivatives include water-soluble cellulose ether derivatives, such as non-ionic and cationic cellulose derivatives. Anionic cellulose derivatives (eg, sodium carboxymethylcellulose) are not included within the definition of cellulose derivatives for purposes of this invention. Nonionic cellulose derivatives are especially preferred. The basic structure of the cellulose derivative is illustrated by the following formula: In the structure, n is an integer on the scale of about 100 to about 10,000, and R 'represents alkyl, hydroxyalkyl, or mixtures of alkyl and hydroxyalkyl substituents, as hereinafter described. Useful alkyl groups include methyl, ethyl, propyl, butyl, pentyl, isobutyl, hexyl, nonyl, and the like. Preferred alkyl groups include methyl, ethyl, propyl and butyl, especially methyl. Preferred hydroxyalkyl groups include hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl, with hydroxybutyl being preferred. Commercially available, highly preferred materials have R 'as mixtures of methyl and hydroxybutyl. A preferred group of cellulose derivatives includes methylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, and mixtures thereof. Examples include METELOSE ™, available from Shin Etsu Co .; METHOCEL ™ from Dow Chemical; C? -C4 alkyl celluloses and C4 hydroxyalkyl celluloses. A preferred cationic cellulose derivative is: C. Additional detergent components 10 The detergent compositions of the invention may also 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 it will be used. Cleaning compositions of the present include, but are not limited to: granular detergents, liquid laundry detergents and the like. Said compositions may contain a variety of conventional detersive ingredients. The following list of such ingredients is for the convenience of the formulator, and not as a limitation of the types of ingredients that can be used with cellulose derivative and branched surfactants in the middle region of your chain. The compositions of the present invention preferably contain one or more additional detergent components selected from surfactants, builders, alkalinity system, organic polymeric compounds, suds suppressants, soil anti-redeposition and suspending agents and corrosion inhibitors.

Bleaching compounds - Bleaching agents and Bleach Activators The detergent compositions herein may also preferably contain bleaching agents or bleaching compositions containing an agent and one or more activators of bleach. bleaching. Bleaching agents are typically found at levels of from about 1% to about 30%, most preferably about 5% to about 20% of the detergent composition, especially for fabric washing. If present, the amount of bleach activators is typically from about 0.1% to about 60%, very typically from about 0.5% to about 40% of the bleaching composition containing the bleaching agent plus the bleach activator. The bleaching agents used herein may be any of the bleaching agents useful for compositions detergents in textile cleaning, hard surface cleaning or other cleaning purposes now known or known later. These include oxygen bleaches as well as other bleaching agents.

Perborate bleaches, for example, sodium perborate (e.g., mono or tetrahydrate) may be used herein. Another category of bleaching agent that can be used without rf restriction comprises percarboxylic acid bleaching agents and the salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and hyperoxydedecanedioic acid. Said bleaching agents are described in Patent of E.U.A. 4,483,781, Hartman, issued November 20, 1984, the Patent Application of E.U.A. 740,446, Burns, et al., Filed June 3, 1985, European Patent Application 0,133,354 Banks, et al., Published February 20, 1985, US Patent. 4,412,934 Chung et al., Issued November 1, 1983. The most preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in the US Patent. 4,634,551 issued on January 6, 1987 to Burns et al. It can also be used peroxygen bleaching agents.

Suitable peroxygen bleach compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide.

Persulfate bleach can also be used (e.g., OXONE, commercially manufactured by DuPont).

A preferred percarbonate bleach comprises dry particles having an average particle size in the range of about 500 microns to about 1,000 microns, no more than F 'about 10% by weight of said particles being smaller than about 200 microns and no more than about 10% by weight of said particles being larger than about 1.250 microns.

Optionally, the percarbonate can be coated with silicate, borate or water-soluble surfactants. Percarbonate is available from several 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 lead to production in situ in the aqueous solution (ie, during the washing process) of the peroxyacid corresponding to the activator. bleaching. Several non-limiting examples of activating faith are described in the U.S. patent. 4,9151, 854 issued on April 10, 1990 to Mao et al., And in the patent of E.U.A. 4,412,934. Typical nonanoyloxybenzenesulfonate (NOBS) and tetraacetylethylamine 20 (TAED) activators and mixtures thereof can also be used. See also E.U.A. 4,634,551 for other typical bleaches and activators useful herein.

The most preferred amido-bleach activators are those of the formulas: R1N (R5) C (0) R2C (0) LO R1C (0) N (R5) R2C (0) L wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms, R2 is an alkylene containing 1 to about 6 carbon atoms, R ^ is H or alkyl, aryl or alkaryl containing from about 1 to about 10 carbon atoms and L is any suitable residual group. A residual group is any group that is displaced from the bleach activator as a result of a nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred residual group is phenyl sulfonate. Preferred examples of bleach activators of the above formulas include (6-octanamido-caproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate and mixtures thereof as described in the patent of E.U.A. 4,634,551 which is incorporated herein by reference. Another class of bleach activators includes activators of the benzoxazine type described by Hodge et al. In the U.S. Patent. 4,966,723 issued October 30, 1990, which is incorporated herein by reference. A highly preferred bleach activator of the benzoxazine type is: Yet another class of preferred bleach activators includes acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulas: wherein R ^ is H or an alkyl, aryl or alkaryl group containing from 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoylcaprolactam, octanoylcaprolactam, 3,5,5-trimethyl-hexanoylcaprolactam, nonanoylcaprolactam, decanoylcapro-lactam, undecenoylcaprolactam, benzoylvalerolactam, octanoylvalerolactam, decanoylvalerolactam, undecenoylvalerolactam, nonanoylvalerolactam, 3,5,5-trimethylhexanoylvalerolactam and mixtures thereof. See also the U.S. Patent. No. 4,545,784 issued to Sanderson on October 8, 1985, incorporated herein by reference, which describes acyl caprolactams, including benzoyl caprolactam, adsorbed on sodium perborate.

Bleaching agents other than oxygen bleaching agents are also known in the art and can be used herein. A type of bleaching agent that is not oxygen of interest ? +% 0 particular includes photoactivated bleaching agents such as sulfonated zinc and / or aluminum phthalocyanines. See U.S. Pat. 4,033,718 issued July 5, 1977 to Holcombe et al. If used, the detergent compositions typically should contain from about 0.025% to about 1.25% by weight of said bleaches, especially sulfonated zinc phthalocyanine. If desired, the bleaching compounds can be catalyzed by means of a manganese compound. Such compounds are well known in the art and include, for example, the manganese-based catalysts described in the U.S.A. No. 5,246,621, patent of E.U.A. No. 5,244,594, patent of E.U.A. No. 5,114,606 and requests for European patents Publication Nos. 549,271 A1, 549,272A1, 544,440A2 and 544. 490A1. Preferred examples of these catalysts include Mn '^ 2 (u- °) 3 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2- (PF6) 2. Mnl '^ u-O) -! (or- OAc) 2 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2- (Cl 4) 2, Mn '4 (u-0) 6 (1, 4,7-triazacyclononane) 4- ( Cl? 4) 2, Mn '"MnI 4 (u-0)? (U-OA O, 4,7-trimethyl-1, 4,7- Triazacyclononane) 2- (Cl 4) 3, Mn'v (1, 4,7-trimethyl-1, 4,7-triazacyclononane) - (OCH 3) 3 (PF) and mixtures thereof. Other metal-based catalysts include those described in the U.S.A. 4,430,243 and patent of E.U.A. 5,114,611. The use of manganese with several complex ligands to improve bleaching is also reported in the following United States 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 practical, and not by way of limitation, the compositions and methods herein can be adjusted to provide in the order of at least one part per ten million of the active bleach catalyst species in the aqueous wash solution, and will preferably provide about 0.1 ppm to about 700 ppm, most preferably about 1 ppm to about 500 ppm of the catalyst species in the wash solution. Cobalt catalysts are known and are useful herein, and are described, for example, in M.L. Tobe, "Base Hydrolysis of Transition-Metal Complexes ", Adv. Inorg. Bioinorg. Mech., (1983), 2, pp. 1-94 The cobalt catalysts which are most preferred and useful herein are cobalt pentaamine acetate salts which have the formula [Co (NH3) 5? Ac] Ty, where "OAc" represents a portion of acetate and "Ty" in an anion, and especially cobalt pentaamine acetate chloride, [Co (NH3) 5OAc] CL2 as well as [Co (NH3) 5OAc] (OAc) 2; [Co (NH3) 5? Ac] (PF6) 2; [Co (NH3) 5OAc] (S04); [Co (NH3) 5? Ac] ( BF4) 2 and [Co (NH3) 5? Ac] (N03) 2 (in the present "CAP"). These cobalt catalysts are readily prepared by known procedures, such as those shown for example in Tobe's article and in the references cited therein, in the US patent 4,810,410 to Diakun et al., Issued March 7, 1989, J. Chem Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, W.L. Jolly (Prentice-Hall; 1970), pp 461-3; Inorg. Chem., 18, 1947-1502 (1979); Inorg. Chem., 21, 2881-2885 (1982); Inorg. Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960) and Journal of Physical Chemistry, 56, 22-25 (1952). As a practical matter, and not by way of limitation, the cleaning compositions and methods herein can be adjusted to provide in the order of at least one part per one hundred million active catalytic bleaching species in the washing medium. aqueous, and will preferably provide about 0.01 ppm to about 25 ppm, most preferably about 0.05 ppm to about 10 ppm and more preferably about 0.1 ppm to about 5 ppm, of the kind of bleach catalyst in the washing solution. To obtain such levels in the washing solution of an automatic washing process, typical compositions herein will comprise from about 0.0005% to about 0.2%, most preferably from about 0.004% to about 0.08% »bleach catalyst, especially manganese or cobalt catalysts, by weight of the cleaning compositions.

Enzymes Enzymes are preferably included in the present detergent compositions for a variety of purposes, including the removal of protein-based stains, based on carbohydrates or triglyceride-based substrates, for the prevention of dye transfer in laundry fabrics, and for fabric restoration. Suitable enzymes include proteases, amylases, cellulases, peroxidases and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast. Preferred selections are influenced by factors such as optimal levels of pH activity and / or stability, thermostability, stability against active detergents, builders, and the like. In this regard, bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases and fungal cellulases. The term "detersive enzyme", as used herein, means any enzyme that has a beneficial effect of cleaning, stain removal or any other beneficial effect in a laundry detergent, hard surface cleaning or personal care composition. Detersive enzymes that are preferred are hydrolases such as proteases and amylases. Enzymes that are preferred for laundry purposes include, but are not limited to, proteases, cellulases and peroxidases. For automatic dishwashing, amylases and / or proteases are preferred, including both commercially available types and improved types, which, while becoming increasingly compatible with the bleach, still have a degree of susceptibility to deactivation of the bleach. Enzymes are normally incorporated in detergent or detergent additive compositions at levels sufficient to provide an "effective cleaning amount". The term "effective cleaning amount" refers to any amount capable of producing a cleaning, stain removal, dirt removal, whiteness, deodorizing or freshness enhancing effect on substrates such as fabrics, tableware and the like. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more typically from about 0.01 mg to about 3 mg, of active enzyme per gram of the detergent composition. Stated otherwise, the compositions herein will typically consist of from about 0.001% to about 5%, preferably 0.01% -1% by weight of a commercial enzyme preparation. Protease enzymes are present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. For certain detergents, such as automatic dishwashing, it may be desirable to increase the active enzyme content of the commercial preparation to minimize the total amount of non-catalytically active materials and thereby improve splashes / films or other results. final. Higher active levels in highly concentrated detergent formulations may also be desirable.

Suitable examples of proteases are subtilisins that are obtained from particular strains of B. subtilis and B. licheniformis. Other suitable proteases are obtained from a Bacillus strain, having a * maximum activity on the whole pH scale from 8 to 12, developed and sold as ESPERASE® by Novo Industries A / S of Denmark, hereinafter "NovoC The preparation of this enzyme and of analog enzymes is described in British Patent No. 1, 243,784, by Novo Other suitable proteases include ALCALASE® and SAVINASE® of Novo and MAXATASE® of International Bio-Synthetics, Inc., The Netherlands; as well as Protease A as the described in EP 130,756 A, January 9, 1985 and Protease B as described in EP 87303761 A, April 28, 1987 and EP 130,756 A, January 9, 1985.

See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes and a reversible protease inhibitor are describe in WO 9203529 A a Novo. Other proteases that are preferred include those of WO 9510591 A to Procter & Gamble. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable in the present is as described in WO 9425583 to Novo. In more detail, a particularly preferred protease, designated "Protease D" is a carbonyl hydrolase variant having an amino acid sequence that is not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to the +76 position, preferably). also in combination with one or more residue positions of amino acids equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265 and / or +274 according to the numeration of the subtilisin of Bacillus amyloliquefaciens, as described in WO 95/10615, published on April 20 of 1995 by Genecor International. Useful proteases are also described in PCT publications: WO 95/30010, published November 9, 1995 by The Procter & Gamble Company; WO 95/30011, published November 9, 1995 by The Procter, & Gamble Company; and WO 95/29979, published November 9, 1995 by The Procter & Gamble Company. Amylases suitable herein, especially for, but not limited to, automatic dishwashing purposes, include, for example, α-amylases described in British Patent No. 1, 296,839 to Novo; RAPIDASE®, International Bio-Synthetics, Inc. and TERMAMYL®, Novo.

FUNGAMYL® by Novo is especially useful. The genetic manipulation of the enzymes is known for improved stability, for example, oxidative stability. See, for example, J. Biological Chem, Vol. 260, No. 11, June 1985, p. 6518-6521. Certain preferred embodiments of the present compositions may make use of amylases having improved stability in detergents such as those used for automatic dishwashing, especially improved oxidative stability as measured against a reference point of TERMAMYL® in commercial use in 1993. These preferred amylases of the present share the characteristics of being "improved stability" amylases, characterized, to a minimum, by a measurable improvement in one or more of: oxidative stability, for example, to hydrogen peroxide / tetraacetylethylene diamine in pH solution regulated at pH 9-10; thermal stability, for example, at common wash temperatures such as about 60 ° C; or alkaline stability, for example, at a pH of about 8 to about 11, measured against the amylase of the reference point identified above. Stability can be measured using any of the technical tests described in the art. See, for example, 'the references described in WO 9402597. The improved stability amylases can be obtained from Novo or Genencor International. An extremely preferred class of amylases herein has the common property of being derived using the site-directed mutagenesis of one or more of the Bacillus amylases, especially the Bacillus alpha-amylases, regardless of whether one, two or multiple strains of Amylases are the immediate precursors. It is preferred to use the oxidative amylases of improved stability vs. the aforementioned reference amylase, especially in the bleaching compositions, most preferably oxygenated bleaching, other than chlorine bleaching, of the present invention.

Said preferred amylases include a) an amylase according to WO 9402597, Novo, Feb. 3, 1994 incorporated above, as further illustrated by a mutant in which it is substituted, using alanine or "t threonine, preferably threonine, the methionine residue located in the position 197 of the alpha-amylase of B. licheniformis, known as TERMAMYL®, or the variation of the homologous position of a similar progenitor amylase, such as B. amyloliquefaciens, B. subtilis, or ß. stearothermophilus; b) improved stability amylases as described by Genencor International in a document entitled "Oxidatively Resistant 10 alpha-Amylases", presented at the 207 American Chemical Society National Meeting, March 13-17, 1944, by C. Mitchinson. It is mentioned that the bleaches in detergents for automatic dishwashing deactivate alpha-amylases, but that oxidative amylases of improved stability have been made by Genencor from B. licheniformis NCIB8061. Methionine (Met) was identified as the residue most likely to be modified. The Met was replaced, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants, particularly important being the variants MI97L and MI97T, being the variant M197T, the variant expressed more stable . The stability was measured in CASCADE® and SUNLIGHT®; c) particularly preferred amylases herein include the amylase variants having further modification in the immediate parent as described in WO 9510603 A and available from the assignee Novo, like DURAMYL®. Another oxidizing amylase of improved stability that is preferred includes that described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other oxidative amylase of improved stability can be used, for example, that derived by mutagenesis. <; directed to mutant, hybrid or simple mutant progenitor forms . known amylases available. Other modifications of enzyme that are preferred are also accessible. See WO 9509909 to Novo. Other amylase enzymes include those described in WO 95/26397 and in the co-pending application by Novo Nordisk PCT / DK96 / 00056. Specific amylase enzymes for use in detergent compositions of the present invention include the alpha-amylases characterized in that they have a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25 ° C to 55 ° C and a pH value in the scale from 8 to 10, measured by the Phadebas® alpha-amylase activity test. (Said alpha-amylase activity test Phadebas® is described on pages 9-10 of WO 95/26397). Also included herein are alpha-amylases that are at least 80% homologous with the amino acid sequences shown in the SEC ID listings in the references. These enzymes are preferably incorporated in the laundry detergent compositions at a level of about 0.00018% to 0.060% pure enzyme by weight of the total composition, preferably about 0.00024% to 0.048% pure enzyme by weight of the total composition.

Cellulases that can be used herein include both bacterial and fungal cellulases, preferably at an optimum pH between 5 and 9.5. The U.S. 4,435,307, Barbesgoard et al., Describes f suitable fungal cellulases of the DSM 1800 strain of Humicola insolens or Humicola, or a cellulase-producing fungus 212 belonging to the genus Aeromonas, and the cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander). Suitable cellulases are also described in GB-A-2,075,028; GB-A-2,095,275 and DE-OS-2,247,832. CAREZYME® and CELLUZYME® (Novo) are especially useful. See also WO 9117243 to Novo. Lipase enzymes suitable for use in detergents are those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19,154, as described in British Patent 1, 372,034. Also see lipases in the Japanese patent application 53,20487, open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipasa P "Amano," or "Amano-P." Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g., Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and Chromobacter viscosum lipases from U.S. Biochemical Corp, E.U.A. and Disoynth Co., Holland and lipases ex Pseudomonas gladioli. The LIPOLASE® enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EP 341, 947) is a preferred lipase for use herein. Lipase and amylase variants stabilized against peroxidase enzymes are presented in WO 9414951 A to Novo. See also WO 9205249 and RD 94359044. Despite the large number of publications about lipase enzymes, only the lipase derived from Humicola lanuginosa and produced in Aspergillus oryzae as a host has so far found wide application as an additive for fabric washing products. This is available from Novo Nordisk under the Lipolase brand, as mentioned previously. To optimize Lipolase's 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 enzyme improves the efficiency in the removal of butter specks by a factor of 4.4 over the wild-type lipase (enzymes compared in a quantity of 0.075. to 2.5 mg of protein per liter). The research description No. 35944, published on March 10, 1994 by Novo Nordisk, discloses that the lipase variant (D96L) can be added in an amount corresponding to 0.001-100 mg (5-500,000 LU / liter) of lipase variant per liter of washing liquid. The present invention provides the benefit of improved whiteness maintenance on fabrics using levels of D96L variant in the detergent compositions containing the branched primary alkyl surfactants in the middle region of their chain in the manner described herein, especially when used D96L at levels on the scale of about 50 LU to about 8500 LU per liter of the wash solution. Suitable cutinase enzymes for use herein are described% in WO 8809367 A to Genencor. 5 Peroxidase enzymes are used in combination with oxygen sources, eg, percarbonate, perborate, hydrogen peroxide, etc., for "bleaching in solution" or to avoid the transfer of dyes or pigments removed from the substrates during operations of washing to other substrates in the washing solution. The known peroxidase enzymes include horseradish peroxidase, ligninase and haloperoxidases such as chloroperoxidase and bromoperoxidase. Peroxidase-containing detergent compositions are described in WO 89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo. , A wide variety of enzyme materials are described and means for their incorporation into synthetic detergent compositions in WO 9307263 A and WO 9307260 A to Genecor International, WO 8908694 A to Novo and US patent. 3,553,139, January 5, 1971 to McCarty and others. Additionally, enzymes are described in the U.S. patent. 4,101, 457, Place et al., July 18, 1978 and in the patent of E.U.A. 4,507,219, Hughes, March 26, 1985. Enzymes useful for detergents can be stabilized by various techniques. Enzyme stabilization techniques are presented and exemplified in the US patent. 3,600,319, August 17, 1971, Gedge et al., EP 199, 405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in E.U. 3,519,570. One Bacillus sp. Useful AC13 which gives proteases, xylanases and cellulases is described in WO 9401532 A to Novo.

Enzyme stabilization system The compositions containing enzymes herein may also 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 stabilization system can be any stabilization system that is compatible with the detersive enzyme. Such a system can be inherently provided by other formulation actives, or can be added separately, for example, by the formulator or by a manufacturer of detergent-ready enzymes. Said enzyme 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 satisfy 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 ions and / or magnesium ions in the finished compositions, which provide said ions to the enzymes. Calcium ions are generally more effective than magnesium ions, and are preferred herein if only one type of cation is being used. Typical detergent compositions will comprise from about 1 to about 30, preferably from about 2 to about 20, most preferably from about 8 to about 12 millimoles % calcium per liter of finished detergent composition, although variation is possible depending on factors including the multiplicity, type and levels of enzymes incorporated. Preferably, the salts of Water-soluble calcium or magnesium, including, for example, calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; very generally, calcium sulfate or the magnesium salts corresponding to the exemplified calcium salts can be used. Further increased levels of calcium and / or magnesium may of course be useful, for example to promote the fat-cutting action of certain types of surfactant. 15 Another approach to stabilization is through the use of borate species. See Severson, E.U.A. 4,537,706. Borate stabilizers, when used, can 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 are suitable. such as borax or orthoborate for the use of detergents. 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 may be possible in the detergent compositions by the use of said substituted boron derivatives.

The stabilization systems of certain cleansing compositions may further comprise from 0 to about 10%, preferably about 0.01% to about 6% by weight, of Chlorine bleach sweepers, added to prevent chlorine bleach species present in many water sources from attacking and deactivating enzymes, especially under alkaline conditions. Although chlorine levels in water can be small, typically on the scale of approximately 0.5 ppm to approximately 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme, for example when washing dishes or fabrics, it can be relatively large; consequently, the stability of the enzyme to chlorine during use is sometimes problematic. Since the percarbonate or perborate, which have the Ability to react with chlorine bleach may be present in some of the present compositions in amounts independent of the stabilization system, the use of additional stabilizers against chlorine may, very generally, not be essential, although improved results may be obtained from its use. Chlorine scavenging anions are widely known and readily available, and, if use, they can be salts containing ammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc. Likewise, antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetraacetic acid (EDTA) or an alkali metal salt thereof, monoethanolamine (MEA) and mixtures thereof can be used. Likewise, special enzyme inhibition systems can be incorporated so that the different enzymes have maximum compatibility. If desired, other conventional sweepers 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 can be used. , formate, lactate, malate, tartrate, salicylate, etc. and mixtures thereof. In general, since the chlorine sweeping function can be carried out by ingredients listed separately under better recognized functions (eg, hydrogen peroxide sources), there is no absolute requirement to add a separate chlorine scavenger unless a compound that performs that function to the desired degree is absent in an embodiment of the invention that contains enzymes; Even in that case, the sweeper is added only for optimal results. In addition, the formulator will exercise a normal chemical ability by avoiding the use of any sweeper or enzyme stabilizer that is primarily incompatible, as formulated, with other reactive ingredients. In connection with the use of ammonium salts, said salts can be simply mixed with the detergent composition, but are prone to adsorb water and / or release ammonia during storage. Accordingly, said materials, if present, are desirably protected in a particle such as that described in E.U.A. 4,652,392, Baginski et al.

Detergency Meters 5 Selected detergency builders of aluminosilicates and silicates are preferably included in the compositions herein, for example to help control mineral hardness, especially Ca and / or Mg in the wash water, or to help the removal of particulate dirt from surfaces. Suitable silicate builders include water-soluble and water-soluble types, and include those having a chain, layer or three-dimensional structure, as well as amorphous-solid or unstructured-liquid types. Alkali metal silicates are preferred, particularly those liquids and solids having a ratio of Yes? 2: Na2? in the scale of 1.6: 1 to 3.2: 1, including, particularly for purposes of automatic dishwashing, solid aqueous silicates of 2 P relationships marketed by PQ Corp. under the BRITESIL® brand, for example, BRITESIL H20; and stratified silicates, for example, those described in U.S. Patent 4,664,839, issued May 12, 1987. to H. P. Rieck. NaSKS-6, sometimes abbreviated "SKS-6", is silicate of crystalline and aluminum-free crystallized d-Na2S05 silicate sold by Hoechst, and is especially preferred in granular laundry compositions. See preparation methods in German Application DE-A-3,417,649 and DE-A-3,742,043. Other layered silicates, such as those having the general formula NaMSix? 2? + I -yH2? wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 may be used herein. Some Other stratified silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 as the alpha, beta and gamma silicate forms. Other silicates can also be used such as for example magnesium silicate, which can serve as a crystallizing agent in granulated formulations, as a stabilizing agent for bleaches, and as a component of foam control systems. Also suitable for use herein are the crystalline ion exchange materials synthesized or hydrates thereof having chain structure and a composition represented by the following general formula in an anhydride form: xM2O.ySiO2.zMO in Where M is Na and / or K, M 'is Ca and / or Mg; y / x is 0.5 to 2.0 and z / x is 0.005 to 1.0 as taught in E.U.A. 5,427,711, Sakaguchi et al., June 27, 1995. Aluminosilicate builders are especially useful in granular detergents, but can also be incorporated into pastes or gels. Suitable for the present purposes are 20 those with the empirical formula: [Mz (Al? 2) z (Si? 2) v] XH2O, where z and v are integers of at least 6, the molar ratio of zav is in the scale from 1.0 to 0.5, and x is an integer from 15 to 264. Aluminosilicates can be crystalline or amorphous, occurring naturally or synthetically derived. An aluminosilicate production method is described in E.U.A. 3,985,669, Krummel et al., October 12, 1976. The preferred synthetic crystalline aluminosilicate ion exchange materials are * f available as Zeolite A, Zeolite P (B), Zeolite X and, as far as possible different from Zeolite P, the so-called Zeolite MAP. Natural types, including clinoptilolite, can be used. Zeolite A has the formula: Na-i2 [(Al? 2) - | 2 (Si? 2) 2] -? H2? wherein x is from about 20 to about 30, especially about 27. Dehydrated zeolites can also be used (x = 0-10). Preferably, the aluminosilicate has a particle size of 0.1-10 microns in diameter. Builders instead of, or in addition to, the silicates and aluminosilicates described hereinabove can optionally be included in the compositions herein to help control the mineral hardness, especially the hardness of Ca and / or Mg in the wash water. or to help the removal of particulate dirt. Detergency builders can function through a variety of mechanisms that • "faith include the formation of soluble or insoluble complexes with hardness ions, by ion exchange and offering a more favorable surface for the precipitation of hardness ions than are the surfaces of the ions. items that are cleaned. The level of builder can vary greatly depending on the final use of the composition and the desired physical form. The builder levels typically comprise at least about 1% builder. The granulated formulations typically comprise from about 10% to about 80%, very typically from 15% to 50% by weight of the detergent composition. Lower or higher levels of detergency builders are not excluded. For example, certain additive formulations of detergent or high surfactant content may not be improved in detergency. The builders suitable herein can be selected from the group consisting of phosphates and polyphosphates, especially the sodium salts, carbonates, bicarbonates, sesquicarbonates, and carbonate minerals other than sodium carbonate or sesquicarbonate; organic mono-, di- and tetracarboxylates, especially the carboxylates which are not water-soluble surfactants and in the form of acid, sodium, potassium or alkanolammonium salts, as well as oligomeric or water-soluble low molecular weight polymeric carboxylates, including the types aliphatic and aromatics; and phytic acid. These may be supplemented with borates, for example, for pH regulation purposes, or by sulfates, especially sodium sulfate and any other fillers or vehicles that may be important for the design of stable detergent compositions containing surfactants and / or builders. of detergency. Mixtures of builders, sometimes called "builders," can be used, and typically comprise two or more conventional builders, optionally supplemented with chelators, pH regulators or fillers, although the latter materials are taken in account separately when describing the quantities of materials herein. In terms of relative amounts of surfactant and builder in the present detergents, the preferred builder systems are typically formulated at a weight ratio of surfactant to builder of from about 60: 1 to about 1: 80 Certain detergents that are preferred have said ratio in the range of 0.90: 1.0 to 4.0: 1.0, preferably 0.95: 1 to 3.0: 1.0. Phosphate-containing builders are commonly preferred when allowed by law, and include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates, exemplified by the tripolyphosphates, pyrophosphates, crystalline polymeric meta-phosphates and phosphonates. Carbonate builders include alkali metal and alkali metal carbonates as described in German Patent Application No. 2,321,001 published November 15, 1973, although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate and other carbonate minerals such as trona or any multiple salts of calcium carbonate such as those having the composition 2Na2C? 3.CaC? 3 when they are anhydrous, and even calcium carbonates including calcite, aragonite and vaterite, especially the forms that have high surface areas relative to compact calcite can be very useful, for example as seeds or for use in synthetic detergent bars. Suitable organic builders include f polycarboxylate compounds, including dicarboxylates and tricarboxylates that are not surfactants and are soluble in water. Very typically, the builder polycarboxylates have a plurality of carboxylate groups, preferably at least 3 carboxylates. The carboxylate builders can be formulated in acid, partially neutral, neutral or overbased form. When they are in salt form, metals are preferred alkalines such as sodium, potassium and lithium, or alkanolammonium salts. Polycarboxylate builders include ether polycarboxylates, such as oxydisuccinate, see Berg, E.U. 3,128,287, April 7, 1964, and Lamberti et al., E.U. 3,635,830, January 18, 1972.

See also builders of "TMS / TDS" from E.U. 4,663,071, Bush and others, May 5, 1987; and other ether polycarboxylates including cyclic and alicyclic compounds, such as those described in,. US patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. Other useful builders include ether hydroxypolycarboxylates, maleic anhydride copolymers with ethylene or vinyl methyl ether, 1,3,5-tri- hydroxybenzene-2,4,6-trisulfonic acid, and carboxymethyloxy-succinic acid, various alkali metal salts , ammonium and substituted ammonium of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as mellitic acid, succinic acid, polymaleic acid, benzene-1, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof. Citrates, for example, citric acid and soluble salts of the • same, they are important detergent builders of carboxylate, for example, for heavy-duty liquid detergents due to their availability from renewable resources and their biodegradability. The citrates can also be used in granular compositions, especially in combination with zeolite and / or layered silicates. Oxydisuccinates are also especially useful in said compositions and combinations.

When allowed and especially in the formulation of bars used for hand washing operations, the alkali metal phosphates such as sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. They may also be used and may have anti-fouling properties - phosphonate builders such as ethan-1-hydroxy-1,1-diphosphonate and other known phosphonates, for example those of E.U.A 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137. m Certain detersive surfactants or their short chain homologues also have detergency builder action. For unambiguous formula reasons, when they have surfactant capacity, these materials are taken into account as detersive surfactants. The preferred types of builder functionality are illustrated by: 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds described in E.U. 4,566,984, Bush, January 28, 1986. Succinic acid builders include alkyl and alkenyl succinic acids of C5-C20 and salts thereof. Succinate builders include: laurisuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Lauryl succinates are described in European patent application 86200690.5 / 0,200,263, published on November 5, 1986. Fatty acids, for example, C- | 2-C- | 8 monocarboxylic acids, can also be incorporated into the compositions as surfactant / builder materials, alone or in combination with the aforementioned builders, especially citrate and / or succinate builders, to provide additional builder activity. Other suitable polycarboxylates are described in E.U. 4,144,226, Crutchfield et al., March 13, 1979 and in E.U.A. 3, 308.067, Diehl, March 7, 1967. See also Diehl, E.U.A. 3,723,322. Other types of inorganic builders materials that can be used have the formula (Mx) Cay (CQ3) 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? = 1-15 (x, multiplied by the valence of M,) + 2y = 2z is satisfied in such a way that the formula have a neutral or "balanced" charge. These builders are called "mineral builders" here. Hydration water or anions other than carbonate can be added, as long as the total charge is balanced or neutral. The load or valence effects of said anions must be added to the correct side of the previous equation. Preferably, a water-soluble cation f selected from the group consisting of hydrogen, metals, is present soluble in water, hydrogen, boron, ammonium, silicon and mixtures thereof, most preferably sodium, potassium, hydrogen, lithium, ammonium and mixtures thereof. Non-limiting examples of non-carbonate anions include those selected from the group consisting of chloride, sulfate, fluoride, oxygen, hydroxide, silicon dioxide, chromate, nitrate, borate and mixtures thereof. same. Detergency builders of this type that are preferred in their simplest forms are selected from the group consisting of Na2? A (C? 3) 2, K2Ca (C03) 2, Na2Ca2 (C? 3) 3, NaKCa (C03) 2 > NaKCa2 (C03) 3, K2Ca2 (C03) 3 and combinations thereof. An especially preferred material for the detergency builder described herein is Na2? A (C? 3) 2 in any of its crystalline modifications. Suitable detergency builders of the type defined above are further illustrated by, and include, the natural or synthetic forms of any or combinations of the following minerals: afganite, andersonite, ashcroftine Y, beyerite, borcharite, burbankite, butschlüta, cancrinite, carbocemaite, carletonita, davina, 20 donnaiita And, fairchildita, ferrisurita, franzinita, gaudefroyita, gaylussita, girvasita, gregorita, jouravskita, kampahaugita And, kettnerita, khanneshita, lepersonitaGd, lyotita, mckelveyita And, microsomita, mroseita, natrofairchildita, nierereita, remonditaCe, sacrofanita, schrockingerita, shortita, surita, tunisita, tuscanita, tirolita, vishnevita or zemkorita. Preferred mineral forms include Niererite, fairchildite and shortita.

Detersive Surfactants The detergent compositions according to the present invention may further comprise preferably additional surfactants, also referred to herein as co-surfactants. It should be understood that the branched chain surfactants prepared in the manner of the present invention can be used individually in cleaning compositions or in combination with other detersive surfactants. Typically, fully formulated cleaning compositions will contain a mixture of surfactant types to obtain broad scale cleaning performance over a variety of soils and stains and under a variety of conditions of use. A The advantage of the branched chain surfactants of the present invention is their ability to be easily formulated in combination with other known types of surfactants. Non-limiting examples of additional surfactants that can be used herein typically at levels of about 1% to about 55% by weight, include the unsaturated sulfates such as oleyl sulfate, the alkylalkoxy sulfates of C < ? o- C- | 8 ("AEXS", especially EO 1-7 ethoxysulfates), alkylalkoxycarboxylates of C-? oC-18 (especially EO 1-5 ethoxycarboxylates), glyceryl esters of C-JQ-C-IQ, alkyl polyglucosides of CJ QCI S and their corresponding sulfated polyglycosides, and alphasulfonated fatty acid esters of C ^ -C-is non-ionic surfactants such as ethoxylated C- | oC- | 8 alcohols and alkylphenols (e.g. , C- | rj-C- | 8 EO (1-10) can also be used If desired, other conventional surfactants such as C-J2-C-J8 betaines and sulphobetaines can also be included in the complete compositions. "sultaines"), amine oxides of C- | j-Ci8 and the like N-alkylpolyhydroxylic acid amides of CJ OCJ S can also be used Typical examples include N-methylglucamides of C-J2-C-I8 - See WO 9,206, 1554. Other surfactants derived from sugar include fatty acid amines of N-alkoxy polyhydroxy, such mo N (3-methoxypropyl) glucamide of C-jo-C-is. The N-propyl to N-hexyl glucamides of C-J2-C-I8 can be used for low foaming, conventional C10-C20 soaps can also be used. If high foaming is desired, the branched chain C- | Q-C- | 6 soaps can be used. Branches of C-10-C14 alkylbenzene sulphonates (LAS) can also be used with the branched surfactants herein., which are commonly used in laundry detergent compositions. A wide range of these surfactant coagents can be used in the detergent compositions of the present invention. A typical list of anionic, nonionic, ampholytic and zwitterionic classes, and species of these surfactant coagents is given in the U.S.A. 3,664,961, issued to Norris on May 23, 1972. Amphoteric surfactants are also described in detail in "Amphoteric Surfactants, Second Edition", E.G. Lomax, Editor (published in 1996 by Marcel Dekker, Inc.) The laundry detergent compositions of the present invention typically comprise from about 0.1% to about 35%, preferably about 0.5% to about 15% by weight surfactant coagents. The selected surfactant coagents are further identified as follows. (1) Anionic surfactant coagents Non-limiting examples of surfactant coagents useful herein typically at levels of from about 0.1% to about 50% by weight, include C- alkylbenzene sulphonates; - | -C- | 8 conventional ("LAS") and C-10-C20 primary alkylsulfonates of branched and random chain ("AS"), the secondary alkyl sulfates (2,3) of C10-C-18 of the formula CH3 (CH2)? (CHOS03-M +) CH3 and CH3 (CH2) and (CHOS03-M +) CH2CH3 where xy (y +1) are integers of at least 7, preferably at least 9, and M is a cation which is solubilized in water, especially sodium, unsaturated sulfates such as oleyl sulfate, the alphasulfonated fatty acid esters of C-JO-C-18 ("AEXS", especially EO 1-7 ethoxysulfates), alkylalkoxycarboxylates of CI QCI S (especially EO 1-5 ethoxycarboxylates). C- | 2-C- | 8 betaines and sulfobetaines ("sultaines"), amine oxides of C-JGJ-C- | 8 and the like can also be included in the overall compositions. Conventional C10-C20 soaps can also be used. If high foaming is desired, soaps of C- | or-C- | 6 of branched chain. Other useful conventional anionic surfactant coagents are listed in conventional texts. The alkoxylated alkylsulphate surfactants herein are water soluble salts or acids of the formula RO (A) mS? 3M wherein R is an unsubstituted C-10-C24 alkyl or hydrocarbyl group having an alkyl component of C10 -C24, preferably an alkyl or hydroxyalkyl of C12-C-I8. most preferably an alkyl or hydroxyalkyl of C 1 -C-J S, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6; most preferably between about 0.5 and about 3, and M is H or a cation which may be, for example, a metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.), an ammonium cation or substituted ammonium. Ethoxylated alkyl sulfates as well as propoxylated alkyl sulphates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and those derivatives of alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like . Exemplary surfactants are polyethoxylated alkyl sulfate (1.0) of C12-C15 (C «j2-Ci5E (1.0) M), polyethoxylated alkyl sulfate (2.25) of C-12-c15 (C-i2-Ci5E (2.25) M), polyethoxylated alkyl sulfate (3.0) of C-12-C15 (C-12- C-) 5E (3.0) M) and polyethoxylated alkyl sulfate (4.0) of C-12-C 5 (C < | 2-Ci 5E (4.0) M) , where M is conveniently selected from sodium and potassium. The alkyl sulfate surfactants herein are water soluble salts or acids of the formula ROSO3M wherein R is preferably C-10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having an alkyl component of CJ OCI S. most preferably alkyl or C-12-C15 hydrocarbyl, and M is H or a cation, for example, an alkali metal cation (eg, sodium, potassium, lithium) or substituted ammonium or ammonium (eg, methyl-, dimethyl cations) and trimethylammonium and quaternary ammonium cations such as tetramethylammonid 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 that can be used are the alkyl ester sulfonate surfactants, including the linear esters of C8-C20 carboxylic acids (ie, fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society, "52 (1975), p 323-329. Suitable starting materials should include fatty acid substances such as derived from tallow, palm and coconut oils, etc.

The preferred alkyl sulfonate ester surfactant, especially for laundry applications, comprises alkyl sulfonate ester surfactants of the structural formula: R -CH (S03M) -C (0) -OR4 wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof, R4 is a hydrocarbyl of C-j-C, preferably an alkyl or combination thereof, and M is a salt-forming cation which forms a water-soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations include metals such as sodium, potassium and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine and triethanolamine. Preferably, R3 is C10-C16 alkyl and R4 is methyl, ethyl or isopropyl. Especially preferred are the methyl estersulfonates wherein R3 is C- | o_C-alkyl. Other anionic surfactant coagents useful for detersive purposes can also 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 salts) of soap, C8-C22 primary or secondary alkanesulfonates, C8-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates for example, as described in British Patent Specification No. 1, 082,179, C 8 -C 24 alkyl polyglycol ether sulphates (containing up to 10 moles of oxide) ethylene); alkylglyceryl sulphonates, fatty acyl glyceryl sulphonates, fatty oleylglyceryl sulfonates, alkylphenolthylene oxide ether sulfates, paraffinsulfonates, "** 'alkyl phosphates, isethionates such as acyl isethionates, N-acyltaurates, alkylsuccinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C-12-C18 monoesters) and sulfosuccinate diesters (especially saturated C6-C-12 diesters and Unsaturated), acyl sarcosinates, alkylpolysaccharide sulfates such as alkylpolyglucoside sulfates (the non-sulfated nonionic compounds described below) and alkylpolyethoxycarboxylates such as those of the formula RO (CH2CH2?) KCH2COO-M + wherein R is a CQ-C22 alkyl. k is an integer from 0 to 10, and M is a soluble salt forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin acids, hydrogenated rosin acids and resin acids and hydrogenated resin acids present in or derived from wood oil. Additional oils are described in "Suface 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. Pat. 3,929,678, issued December 30, 1975 Laughiin and others in the Column 23, line 58 to column 29, line 13 (incorporated herein by reference). A preferred disulfate surfactant has the formula: # ** "9 wherein R is an alkyl group, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide of chain length of C- | to C28, preferably C3 to C24, most preferably Cs to C20 or hydrogen; A and B are independently selected from alkyl, substituted alkyl and alkenyl groups of C < | to C28, preferably C-j to C5, most preferably C- | or C2, or a covalent bond, and A and B contain in total at least 2 atoms; A, B and R contain in total from 4 to about 31 carbon atoms; X and are anionic groups selected from the group consisting of sulfate and sulfonate, provided that at least one of X and Y is a sulfate group, and M is a cationic moiety, preferably one of substituted or unsubstituted ammonium, or an alkaline or alkaline earth metal. The most preferred disulfate surfactant has the formula as above wherein R is an alkyl group of chain length of C <;? or to C- | 8, and B are independently C- | or C2, both X and Y are sulphate groups and M is one of potassium, ammonium or sodium. The disulfate surfactant is typically present at levels of incorporation from about 0.1% to about 50%, preferably from about 0.1% to about 35%, most preferably from about 0.5% to about 15% by weight of the detergent composition.

The disulfate surfactant which is preferred herein includes: (a) 1,3-disulfate compounds, preferably 1,3-disulfonates * f straight or branched alkyl or alkenyl of C7-C23 (i.e. 'total number of carbons in the molecule), which most preferably have the formula: Wherein R is a straight or branched alkyl or alkenyl group of chain length from about C4 to about C- | 8; (b) 1-4-disulfate compounds, preferably 1,4-C22 straight or branched chain alkyl or alkenyl disulfates, which most preferably have the formula: wherein R is a straight or branched alkyl or alkenyl group of chain length from about C4 to about C-J S; the preferred R Is selected from octanyl, nonanyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and mixtures thereof; and (c) 1,5-disulphate compounds, preferably 1,4-C23 straight or branched chain alkyl or alkenyl disulfates, which most preferably have the formula: x x mo3-M + wherein R is a straight or branched alkyl or alkenyl group of chain length from about C4 to about C- | 8- The known syntheses of certain disulfated surfactants generally use an alkyl or alkenyl succinic anhydride as the main material of p ^ artida. This is initially subjected to a reduction step from which a diol is obtained. Subsequently, the diol is subjected to a sulfation step to give the disulfated product. As an example, US-A-3, 634,269 discloses 2-alkyl or alkenyl-1,4-butanediol disulfates prepared by reducing alkenyl succinic anhydrides with lithium aluminum hydride to produce alkyl or alkenyl diols which are then sulfated. In addition, US-A-3,959,334 and US-A-4,000,081 disclose 2-hydrocarbyl-1,4-butanedioldisulfates also prepared using a method that includes the reduction of alkenyl succinic anhydrides with lithium aluminum hydride to produce alkyl or alkenyl diols which are then sulfated. See also US-A-3,832,408 and US-A-3,860,625, which describe ethoxylated 2-alkyl or alkenyl-1,4-butanediol disulphates prepared by reducing alkenyl succinic anhydrides with lithium aluminum hydride to produce alkyl or alkenyl diols which are then ethoxylated before sulfation. These compounds can also be made by a method that includes the synthesis of the disulfate surfactant from a substituted cyclic anhydride having one or more substituents on the carbon chain with a total of at least 5 carbon atoms comprising the following steps : (i) reduction of said substituted cyclic anhydride to form a diol; and (ii) sulfation of said diol to form a disulfate, wherein said reduction step comprises hydrogenation under pressure in the presence of a hydrogenation catalyst containing a transition metal. When included therein, 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 an anionic surfactant. (2) Nonionic surfactant coagents Non-limiting examples of nonionic surfactant coagents useful herein typically at levels of from about 0.1% to about 50% by weight, include alkoxylated alcohols (AE's) and alkylphenols, polyhydroxy fatty acid amides. (PFAA's), alkyl polyglycosides (APG's), glycerol esters of C-J O-C-I S and the like. Very specifically, the condensation products of primary and secondary aliphatic alcohols containing from about 1 to about 25 moles of ethylene oxide (AE) are suitable for use as the nonionic surfactant in the present invention. The alkyl chain of the aliphatic alcohol may be straight or branched, primary or secondary, and generally contains about 8 to about 22 carbon atoms. Preferred are the condensation products of alcohols having an alkyl group containing from about 8 to about 20 carbon atoms, most preferably from about 10 to about 18 carbon atoms, with from about 1 to about 10 moles, preferably 2 to 7, most preferably 2 to ethylene oxide per mole of alcohol. Especially preferred nonionic surfactants of this type are the ethoxylated C9-C15 primary alcohols containing 3-12 moles of ethylene oxide per mole of alcohol, particularly the primary C12-C15 alcohols containing 5-10 moles of oxide of ethylene per mole of alcohol. Examples of commercially available nonionic surfactants of this type include Tergitol ™ 15-S-9 (the condensation product of C11-C15 linear secondary alcohol with 9 moles of oxide). of ethylene), Tergitol ™ 24-L-6 NMW (the primary alcohol condensation product of C-12-C14 of 6 moles of ethylene oxide with a narrow molecular weight solution), both marketed by Union Carbide Corporation; Neodol ^ 45.9 (e | linear condensation product of C14-C-15 with 9 moles of ethylene oxide), Neodol ^ M 23-3 (the linear condensation product of C-12-C13 with 3 moles of ethylene oxide), NeodofTM 45.7 (e | linear C14-C15 alcohol condensation product with 7. moles of ethylene oxide), Neodol ^ M 45.5 (e | linear C14-C15 alcohol condensation product with 5 moles of ethylene oxide), marketed by Shell Chemical Company; KyroTM EOB (the condensation product of C-13-C-15 alcohol with 9 moles of ethylene oxide), marketed by The Procter & Gamble Company; and Genapol LA 030 u 050 (the condensation product of C 12 -C 14 alcohol with 3 or 5 moles of ethylene oxide), marketed by Hoechst. The preferred HLB scale in these nonionic surfactants of AE is 8-17 and more preferred is 8-14. Condensates with propylene oxide and butylene oxides can also be used. Another class of nonionic surfactant coagents which is preferred to be used herein are the polyhydroxy fatty acid amide surfactants of the formula: wherein R1 is H, or C-1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R2 is C5-31 hydrocarbyl and z is polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, R 1 is methyl, R 2 is a straight chain C 1 -C 4 alkyl, or a C 15 -C 17 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose and lactose in a reductive amination reaction Typical examples include C 2 -C 18 and C 12 -C 14 N-methyl glucamides See US 5,194,639 and 5,298,636 N-alkoxy polyhydroxylic acid amides can also be used see EUA ,489,393. Also useful as a nonionic surfactant coagent in the present invention are the alkyl polysaccharides such as those described in the U.S.A. No. 4,565,647, Filling, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms, preferably from about 10 to about 16 carbon atoms, and a polysaccharide, e.g., a group polyglycoside hydrophilic containing from about 1.3 to about 10, preferably from about 1.3 to about 3, more preferably from about 1.3 to about 2.7 units of saccharide. Any reducing saccharide containing 5 or 6 carbon atoms can be used, for example, the portions of glucose, galactose and galactosyl can be substituted by the glucosyl portions (optionally the hydrophilic group is attached in the 2-, 3-, 4- positions -, etc., thus giving a Q glucose or galactose as opposed to a glucoside or galactoside). The saccharide bonds 5 can be, for example, between position one of the additional saccharide units and positions 2, 3, 4 and / or 6 in the preceding saccharide units. Preferred alkyl polyglycosides have the formula R20 (CnH2nO) t (glucosyl) x Wherein R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14 carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, Preferably, 0; and x is from about 1.3 to about 10, preferably about 1.3 to about 3, very ™ preferably from about 1.3 to about 2.7. The glucosyl is preferably derived from glucose. To prepare these compounds, alcohol or alkylpolyethoxylated alcohol is formed first, and then it is made react with glucose or a source of glucose to form the glucoside (fixation at position 1). The additional glucosyl units can then be fixed between their position 1 and the preceding glucosyl units in the 2-, 3-, 4- and / or 6- position, preferably predominantly in the 2-position. Compounds of this type and their use in detergents are described in EP-B 0 070 077, 0 075 996 and 0 094 118. The condensates of polyethylene oxide, polypropylene and polybutylene of alkylphenols are suitable for use as the agent nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being more preferred. These compounds include the condensation products of alkylphenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from About 8 to about 14 carbon atoms, either in a straight chain or branched chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to from about 2 to about 25 moles, most preferably from about 3 to about 15 moles, of ethylene oxide per mole of alkylphenol. Commercially available nonionic surfactants of this type include IgepafT CO-630, marketed by GAF Corporation; and Triton ™ X-45, X-114, X-100 and X-102, all sold by Rohm & Haas Company. These surfactants are commonly known as alkylphenol alkoxylates (for example, ethoxylates of alkylphenol). The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant system of the present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800, and will exhibit insolubility in water. The addition of portions of polyoxethylene to this hydrophobic portion tends to increase the water solubility of the molecule as a whole. Examples of compounds of this type include certain Pluronic ™ M surfactants commercially available and 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 excess propylene oxide, and generally has a molecular weight of about 2500 to about 3000. This hydrophobic portion is condensed with ethylene oxide to the extent that the condensation product * contains from about 40% to about 80% in weight of polyoxyethylene and has a molecular weight of from about 5000 to approximately 11,000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic ™ compounds, marketed by BASF. Nonionic surfactants which are also preferred are the amine oxide surfactants. The compositions of the present invention may comprise amine oxide according to general formula I: F R (EO) x (PO) and (BO) zN (0) (CH2R,) 2.qH2? (I) In general, it can be seen that structure (I) provides a long chain Rl (EO) x (PO) and (BO) z portion and two short chain CH2R 'portions. R 'is preferably selected from hydrogen, methyl and -CH2OH. In general R ^ is a primary or branched hydrocarbyl portion that can be saturated or unsaturated, preferably R "is a primary alkyl portion When x + y + z = 0, R1 is a hydrocarbyl portion having a chain length of about 8 to about 18. When x + y + z is different from 0, R ^ can be a little longer, the chain length of C12-C24 having a chain length. The general formula also covers amine oxides in which x + y + z = 0, R? = C8-C18, R-H and q = 0-2,? Preferably 2. These amine oxides are illustrated by C12-C14 alkyldimethylamine oxide, hexadecyldimethylamine oxide, octadecylamine oxide and its hydrates, especially dihydrates such as those described in US Pat. 5,075,501 and 5,071, 594, incorporated herein by reference. The invention also encompasses amine oxides in which x + y + z is nonzero, specifically x + y + z is from about 1 to about 10, R1 is a primary alkyl group containing 8 to about 24 carbons, preferably from about 12 to about 15 carbon atoms; in these embodiments y + z is preferably 0 and x is preferably from about 1 to about 6, most preferably from about 2 to about 4; EO represents ethyleneoxy; PO represents propyleneoxy; and BO represents butyleneoxy. Said amine oxides can be prepared by conventional synthetic methods, for example, by conventional synthetic methods, for example, by reacting alkyl ethoxy sulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide. The highly preferred amine oxides herein are the solutions at room temperature. Amine oxides suitable for use herein are commercially manufactured by a number of suppliers, including Akzo Chemie, Ethyl Corp. and Procter & Gamble.

See the McCutcheon compilation and the Kirk-Othmer article for alternative amine oxide manufacturers. Although in certain preferred embodiments R 'is H, there is a certain latitude with respect to having R' slightly larger than H. Specifically, the invention further encompasses embodiments in which R 'is CH2OH, such as hexadecylbis oxide (2- hydroxyethyl) amine, sebobis (2-hydroxyethyl) amine oxide, stearylbis (2-hydroxyethyl) amine oxide, oleylbis (2-hydroxyethyl) amine oxide and dodecyldimethylamine dihydrate oxide. (3) Cationic Surfactant Coagents Non-limiting examples of cationic surfactant coagents useful herein typically at levels of about 0.1% a about 50% by weight, include the choline ester quats and the alkoxylated quaternary ammonium surfactant compounds (AQA), and the like. The cationic surfactant coagents useful as a component of the surfactant system is a cationic choline ester quat surfactant which are preferably water dispersible compounds having surfactant properties and comprising at least one ester linkage (i.e. -COO-) and at least one cationically charged group. Suitable cationic ester surfactants, including choline ester surfactants, are described, for example, in U.S. Patents. Nos. 4,228,042, 4,239,660 and 15 4,260,529. Preferred cationic ester surfactants are those having the formula: wherein R is a linear or branched C5-C31 alkyl, alkenyl or alkaryl chain 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, OCONH or NHCOO; R2, R3, R4, RQ, R7 and Rd 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 a C1-C3 alkyl group; where the values of m, n, syt are independently on the scale from 0 to 8, the value of b is on the scale from 0 to 20, and the values of a, u and v are independently either 0 or 1, with the proviso that at least one of uov is 1; and where M is a counter anion. Preferably, R2, R3 and R4 are independently selected from QH3 and -CH2CH2OH. Preferably, M is selected from the group consisting of halide, methyl sulfate, sulfate and nitrate, most preferably methyl sulfate, chloride, bromide or iodide. Preferred water-dispersible cationic ester surfactants are choline esters having the formula: wherein R1 is a linear or branched C1-C19 alkyl chain. Particularly preferred choline esters of this type include the quaternary methylammonium halides of stearoyl choline ester (R = C17 alkyl), the quaternary methylammonium halides of palmitoyl choline ester (R1 = C5 alkyl), the halogenides of myristoyl choline ester quaternary methylammonium (R1 = C13 alkyl), the halides S \ f of quaternary methylammonium ester of lauroyl choline (R * = Cu alkyl), cocoyl choline ester quaternary methylammonium halides (R1 = C1-C13 alkyl), quaternary methylammonium halides of seboyl choline ester (R1 = C15-C7 alkyl) and any mixture thereof. The particularly preferred and above-mentioned choline esters 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, water, propylene glycol or preferably an ethoxylated fatty alcohol such as ethoxylated C 10 -C 8 fatty alcohol having a degree of ethoxylation of from 3 to 50 ethoxy groups per mole forming the desired cationic material. They can also be prepared by the direct esterification of a long chain fatty acid of the desired chain length together with 2-haloethanol, in the presence of an acid catalyst material. The reaction product is subsequently quaternized with trimethylamine, forming the desired cationic material. Other suitable cationic ester surfactants have the following structural formulas, wherein d can be from 0 to 20.

£ * In a preferred aspect, these cationic ester surfactants are hydrolysable under the conditions of a laundry washing method. Cationic surfactant coagents useful herein also include the alkoxylated quaternary ammonium surfactant compounds (AQA) (hereinafter referred to 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 about 10 to about 16 carbon atoms, more preferably about 10 to about 14 carbon atoms; R2 is an alkyl group containing 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, methylisulfate, sulfate or the like, sufficient to provide electrical neutrality. A and A 'may vary independently and % 9 each select C1-C4 alkoxy, especially ethoxy (i.e., -5 CH2CH2O-), propoxy, butoxy and ethoxy / propoxy mixed; p is from 0 to about 30, preferably 1 to about 4 and q is from 0 to about 30, preferably 1 to about 4 and more preferably about 4; preferably p and q are 1. See also: EP 2,084, published May 30, 1979 by The Procter & Gamble 10 Company, which describes cationic surfactant coagents of this type that are also useful herein. The AQA compounds in which the hydrocarbyl substituent R1 is C8-C1, especially C Q, increase the dissolution rate of the laundry granules, especially under cold water conditions, in comparison with the highest chain length materials. Accordingly, the AQA surfactants of Cs-Cn may be preferred C by some formulators. The levels of AQA surfactants used to prepare the finished laundry detergent compositions can vary from about 0.1% to about 5%, typically from about 0.45% to about 2.5% by weight. In accordance with the foregoing, the following are non-limiting and specific illustrations of AQA surfactants used herein. It is to be understood that the degree of alkoxylation mentioned 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. From this way, it is not uncommon to report total EO values that are not whole numbers, for example, "E02.5", "E03.5" and the like.

Designation Rl B? ApR3 A'gR4 AQA-1 C12-O14 CH3 EO EO (also called cocometil E02) AQA-2 C12-C16 CH3 (EO) 2 EO AQA-3 O 2-C14 CH3 (EO) 2 (EO) 2 (cocometil E04 ) AQA-4 012 CH3 EO EO AQA-5 'O12-C14 CH3 (EO) 2 (EO) 3 AQA-6 O12-C14 CH3 (EO) 2 (EO) 3 AQA-7 C8-C 8 CH3 (EO) 3 (EO) 2 AQA-8 C12-C14 CH3 (EO) 4 (EO) 4 AQA-9 C12-C14 C2H5 (EO) 3 (EO) 3 AQA-10 012-018 C3H7 (EO) 3 (EO) 4 AQA-11 012-018 CH3 (propoxy) (EO) 3 AQA-12 C 0-Ci 8 C2H5 (iso- (EO) 3 propoxy) 2 AQA-13 C10-C 8 CH3 (EO / PO) 2 (EO ) 3 AQA-14 C8-C 8 CH3 (EO) 15 * (EO) 5 * Designation Rl R? ApR3 A'qR4 AQA-15 c10 CH3 EO EO AQA-16 C8-C12 CH3 EO EO AQA-17 C9-C CH3-EO 3.5 avg. - AQA- 18 C12 CH3 - EO 3.5 avg. - AQA- 19 C8-C14 CH3 (EO) 1 0 (EO)? 0 AQA-20 O10 C2H5 (EO) 2 (EO) 3 AQA-21 C 2-C 4 C2H5 (EO) 5 (EO) 3 AQA-22 C 2-C18 C3H7 Bu (EO) 2 Ethoxy, blocked at the ends optionally with methyl or ethyl. The bis-ethoxylated cationic surfactants which are / are preferred herein are available under the ETHOQUAD brand from Akzo Nobel Chemicals Company. The highly preferred bis-AQA compounds to be used herein have the formula: wherein R1 is a C10-C8 hydrocarbyl and mixtures thereof, preferably alkyl of CI Q, C12 and C14 and mixtures thereof, and X is any convenient anion that provides charge balance, preferably chloride. With reference to the general AQA structure shown above, since in a preferred compound R1 is derived from coconut fraction fatty acids (C12-C14 alkyl), R2 is methyl and ApR3 and A'qR4 are each monoethoxy, this Preferred type of compound is called here "CocoMeE02" or "AQA-1" in the above list. Other AQA compounds that are preferred herein include the compounds of the formula: wherein R1 is hydrocarbyl of CI Q-CI S, preferably C10-C14 alkyl, p is independently 1 to about 3 and q is from 1 to about 3, R2 is C1-C3 alkyl, preferably methyl and X is an anion, especially chloride. Other compounds of the above type include those in which the ethoxy units (CH2CH2O) (EO) are replaced by butoxy units (Bu), isopropoxy [CH (CH3) CH2?] And [CH2CH (CH3?] (-Pr) or n-propoxy (Pr), or mixtures of units EO and / or Pr and / or ¡-Pr. The following illustrates several other auxiliary ingredients that may be used in the compositions of this invention, but are not intended to be limiting thereof. Although the combination of the branched alkyl primary surfactants in the middle region of their chain with said auxiliary compositional ingredients can be provided as finished products in the form of gels, sticks or the like using conventional techniques, the manufacture of granular laundry detergents from the present requires certain special processing techniques in order to achieve optimum performance. Accordingly, the manufacture of detergent granules will be described hereinafter and separately in the Granule Manufacturing section (below), for the convenience of the formulator. Additional cationic surfactant coagents are disclosed in, for example, "Surfactant Science Series," Volume 4, "Cationic Surfactants" or "Industrial Surfactants Handbook." The useful classes of cationic surfactants described in these references include amide cuats (i.e. Lexquat AMG & Schercoquat CAS), glycidyl ether cuats (ie, Cyostat 609), hydroxyalkyl (ie Dehyquart E), alkoxypropyl (ie Tomah Q-17-2), polypropoxy (Emcol CC-9) cuats, cyclic alkylammonium compounds (ie say, pyridinium or imidazolinium cuats) and / or benzalkonium cuats.

Polymeric dirt release agent Polymeric soil release agents known, hereinafter "SRA" or "SRA's", can optionally be employed in the present detergent compositions. If used, the SRA's will generally comprise from about 0.01% to 10.0%, typically from about 0.1% to 5%, preferably from about 0.2% to 3.0% by weight, of the composition. Preferred SRA's typically have hydrophilic segments f to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and the hydrophobic segments to be deposited on hydrophobic fibers and remain adhered to them through the conclusion of the washing and rinsing cycles, thus serving as an anchor for the hydrophilic segments. This can make it possible for spots that occur after treatment with the SRA to be cleansed more easily in the subsequent washing procedures. SRA's may include a variety of charged species, eg, anionic or even cationic (see U.S. Patent No. 4,956,447), as well as uncharged monomer units and their structures that can be linear, branched and even in the form of star They may include end blocking portions that are especially effective in controlling molecular weight or altering active surface or physical properties. The structures and load distributions can be designed for application to different types of fibers or textiles and for detergent products or various detergent additives.

Preferred SRA's include oligomeric terephthalate esters, typically prepared by methods that include at least one transesterification / oligomerization, commonly with a metal catalyst such as a titanium (IV) alkoxide. Said esters can be manufactured using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without, of course, forming a dense f entangled overall structure. Suitable SRA's include: a sulphonated product of a substantially linear ester oligomer formed from an oligomeric ester base structure of terephthaloyl and oxyalkylenoxy repeat units and sulfonated terminal portions derived from allyl covalently bonded to the base structure, eg, as described in the US patent 10 4,968,451, November 6, 1990 by J. J. Scheibel and E.P. Gosselink: said ester oligomers can be prepared (a) by ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in a two step transesterification / oligomerization process; and (c) reacting the product of (b) with sodium metabisulfite in water; the polyesters of 1, 2-propylene / polyoxyethylene terephthalate of non-ionic blocked ends of the U.S. patent. No. 4,711, 730, of December 8, 1987 to Gosselink et al., For example those produced by the transesterification / oligomerization of polyethylene glycol methyl ether, DMT, PG and poly (ethylene glycol) ("PEG"); the oligomeric esters of anionic blocked ends partially and completely of the U.S. patent. No. 4,721, 580, from January 26, 1988 to Gosselink, such as oligomers of ethylene glycol ("EG"), PG, DMT and sodium 3,6-d-oxa-8-hydroxy octane sulfonate; the non-ionic blocked block polyester oligomeric compounds of the U.S.A. 4,702,857, from October 27, 1987 to Gosselink, for example produced from DMT, PEG and EG and / or PG (Me) -blocked from f methyl or a combination of DMT, EG and / or PG, Me-blocked PEG and sodium dimethyl-5-sulfoisophthalate; and the blocked terephthalate esters of the anionic ends, especially of sulfoaroyl of the U.S. patent. Do not. 4,877,896 of October 31, 1989 to Maldonado, Gosselink and others, the latter being a typical SRA's useful both in fabric conditioning and laundry products being an example an ester composition made from the monosodium salt of m-sulfobenzoic acid, PG and DMT, optionally but preferably further comprising added PEG, eg, PEG 3400. SRA's also include: simple copolymer blocks of ethylene terephthalate or propylene terephthalate with terephthalate polyethylene oxide or polypropylene oxide, see US patent No. 3,959,230 to Hays of May 25, 1976 and the patent of E.U.A. No. 3,893,929 to Basadur, July 8, 1975. Suitable SRA's characterized by hydrophobic polyvinylmethyl ether segments include polyvinyl ether graft copolymers, for example, C? -20 C vinyl ethers, preferably poly (vinylacetate), grafted onto polyalkylene oxide base structures. See European patent application 0 219 048, published on April 22, 1987 by Kud et al. Commercially available examples include SOKALAN SRA's such as SOKALAN HP-22, available from BASF, Germany. Other SRA's are polyesters with repeating units having 10-15% by weight of ethylene terephthalate together with 90-80% by weight of polyoxyethylene terephthalate derived from polyoxyethylene glycol of an average molecular weight of 300-5,000. Commercial examples include ZELCON 5126 from Dupont and MILEASE T from ICI. Another preferred SRA is an oligomer having the empirical formula (CAP) 2 (EG / PG) 5 (T) 5 (SIP) ?, which comprises terephthaloyl units (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG / PG), and which preferably terminates with end blocks (CAP), preferably modified isethionates, as in an oligomer comprising a unit sulfoisophthaloyl, 5 terephthaloyl units, oxyethyleneoxy and oxy-1, 2-propyleneoxy units in a defined ratio, preferably from about 0.5: 1 to about 10: 1, and two end-blocking units derived from 2- (2-hydroxyethoxy) -etansulfonate. Said SRA preferably comprises from 0.5% to 20% by weight of the oligomer of a crystallinity reduction stabilizer, for example an anionic surfactant such as linear dodecylbenzenesulfonate or a member selected from xylene-, cumen- and toluenesulfonate or mixtures thereof, these stabilizers or modifiers being introduced into the synthesis vessel, all as taught in the US patent No. 5,415,807, Gosselink, Pan, Kellett and Hall, issued May 16, 1995. Suitable monomers for the above SRA include sodium 2- (2-hydroxyethoxy) -ethansulfonate, DMT, sodium dimethyl-5-sulfoisophthalate, EG and PG.

Yet another group of preferred SRA's are oligomeric esters comprising: (1) a base structure comprising (a) at least one unit selected from the group consisting of dihydroxysulfonates, P polyhydroxysulfonates, a unit which is at least trifunctional, medium of which ester bonds resulting in a branched oligomeric base structure, and combinations thereof, are formed; (b) at least one unit that is a terephthaloyl moiety; and (c) at least one non-sulfonated unit which is a 1,2-oxyalkylenoxy portion; and (2) one or more blocking units selected from non-ionic blocking units, units of Anionic blocking agents such as alkoxylated isethionates, preferably ethoxylated, alkoxylated propansulfonates, alkoxylated propandisulfonates, alkoxylated phenolsulfonates, sulfoaroyl derivatives, and mixtures thereof. The esters of the empirical formula are preferred:. { (CAP) x (EG / PG) and '(DEG) and "(PEG) and"' (T) z (SIP) z '(SEG) q (B) m} Wherein CAP, EG / PG, PEG, T and SIP are as defined above, (DEG) represents units of di (oxyethylene) oxy; (SEG) represents units derived from glycerin sulfoethyl ether and related portion units; (B) represents branching units which are at least trifunctional, by means of which ester bonds are formed which result in a base structure of branched oligomer; x is from about 1 to about 12; and 'is from about 0.5 to about 25; and "is from 0 to about 12, and '" is from 0 to about 10, and' + y "+ y '" sum total of about 0.5 to about 25; z is from about 1.5 to about 25; z 'is from about 0 to about 12; z + z 'sum total of about 1.5 to about 25; q is around 0.05 to about 12; m is around 0.01 a (f about 10, and x, y ', y ", y'", z, z ', q and m represent the number average of moles of the corresponding units per mole of said ester, and said ester has a molecular weight ranging from about 500 to about 5,000. Preferred SEG and CAP monomers for the above esters include sodium 2- (2,3-dihydroxypropoxy) ethane sulfonate ("SEG"), 2-10. { 2- (2-hydroxyethoxy) ethoxy} sodium acetate sulfonate ("SE3") and homologues and mixtures thereof, and the products of ethoxylation and sulphonation of allylic alcohol.

Preferred SRA esters in this class include the transesterification and oligomerization product of 2-. { 2- (2-hydroxyethoxy) ethoxy} sodium ethane sulfonate and / or 2- [2-. { 2- (2-hydroxyethoxy) ethoxy} sodium ethoxy] ethane sulfonate, DMT, 2- (2,3-dihydroxypropoxy) ethane sulfonate, EG and PG using an appropriate Ti (IV) catalyst, and can be designated as "* (CAP) 2 (T) 5 (EG / PG) 1.4 (SEG) 2.5 (B) 0.13, where CAP is (Na + -? 3S [CH2CH2?] 3.5) - and B is a glycerin unit, and the molar ratio of EG / PG is approximately 1.7: 1 measured by conventional gas chromatography after complete hydrolysis. Additional classes of SRA's include: (I) non-ionic terephthalates using diisocyanate coupling agents to link the polymeric ester structures, see E.U.A. 4,201, 824, Violland et al. And E.U.A. 4,240,918 Lagasse et al .; (II) SRA's with carboxylate end groups made by adding trimethyl ahydride to known SRA's for converting terminal hydroxyl groups to trimethylate esters. With the proper selection of the catalyst, trimethyl anhydride forms bonds to the polymer terminals through a carboxylic acid ester isolated from the trimethyl anhydride instead of opening the anhydride linkage. Either non-ionic or anionic SRAs can be used as starting materials, as long as they have hydroxyl end groups that can be esterified, see E.U.A. No. 4,525,524 Tung et al .; (III) Non-anionic terephthalate-based SRAs of the urethane-linked variety, see E.U.A. 4,201, 824, Violland et al .; (IV) poly (vinylcaprolactam) and copolymers related to monomers such as vinylpyrrolidone and / or dimethylaminoethyl methacrylate, including nonionic and cationic polymers, see E.U.A. 4,579,681, Rupper et al; (V) graft copolymers, in addition to SOKALAN types of BASF, manufactured by grafting acrylic monomers to sulfonated polyesters; these SRA's have soil release and anti-redo activity similar to the known cellulose ethers: see EP 279,134 A, 1988 to Rhone-Poulenec Chemie; (VI) vinyl monomer grafts such as acrylic acid and vinyl acetate in proteins such as caseins, see EP 457,205 A to BASF (1991); (VII) Polyester-polyamide SRA's prepared by condensing adipic acid, caprolactam and polyethylene glycol, especially for treating polyamide fabrics, see Bevan et al., DE 2,335,044 to Unilever N.V., 1974. Other useful SRA's are presented in the U.S. Patents. Nos. 4,240,918, 4,787,989 and 4,525,524 and 4,877,896. f i Clay dirt removal / anti-redeposition agents The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having clay dirt removal and anti-redeposition properties. Granular detergent compositions containing these compounds typically comprise from about 0.01% to about 10.0% by weight of the water-soluble ethoxylated amines; Liquid detergent compositions typically contain from about 0.01% to about 5%. The most preferred soil remover and anti-redeposition agent is ethoxylated tetraethylenepentamine. The ethoxylated amines copies are more fully described in the US patent. 4,597,898, VanderMeer, issued July 1, 1986. Another group of clay soil removal / anti-redeposition agents are the cationic compounds described in European patent application 111, 965, Oh and Gosselink, published on June 27, 1984. Other clay removers / anti-redeposition agents that can be used include the ethoxylated amine polymers described in European patent application 111, 984, Gosselink, published June 27, 1984; the zwitterionic polymers described in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides described in the U.S.A. No. 4,548,744, Connor, issued October 22, 1985. Other clay removers and / or anti-redeposition agents known in the art can be used in the compositions herein. patent of E.U.A. 4,891, 160, VanderMeer, issued January 2, 1990 and WO 95/32272, published November 30, 1995.

Polymer dispersion agents Polymer dispersion agents can be used advantageously at levels of from about 0.1% to about 7%, by weight, in the compositions herein, especially in the presence of zeolite builders and / or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art may also be used. technique. It is believed, although not intended to be limited by theory, that polymer dispersion agents increase the performance of the improver Global detergency C, when used in combination with other detergency builders (including lower molecular weight polycarboxylates) by inhibition of crystal growth, peptization of soil release in particles and anti-redeposition. Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing 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, • 0 methylenemalonic acid. The presence of the polymeric polycarboxylates in the The present or polymeric segments, which do not contain carboxylate radicals such as vinyl methyl ether, styrene, ethylene, etc., are suitable provided that said segments do not constitute more than about 40% by weight. Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Said polymers based on acrylic acid which are useful herein are the water soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form perferably varies from about 2,000 to 10,000, most preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000. The water-soluble salts of said polymers Acrylic acid may include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. The use of polyacrylates of this type in detergent compositions has been presented, for example, in Diehl, patent . of E.U.A. 3,308,067, issued March 7, 1967. Acrylic / maleic acid-based copolymers can also be used as a preferred component of the dispersing / anti-redeposition agent. Such materials include the water soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of said copolymers in the acid form preferably varies from about 2,000 to 100,000, more preferably around 5,000 to 75,000 and most preferably around 7,000 to 65,000. The relationship of the segments of Acrylate with respect to those of maleate in said copolymers generally varies of about 30: 1 to about 1: 1, most preferably about 10: 1 to 2: 1. The water soluble salts of said acrylic acid / maleic acid copolymers may include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate / maleate copolymers of this type are known materials which are described in the patent application European No.66915, published on December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also discloses polymers comprising hydroxypropylacrylate. Other useful dispersing agents include the terpolymers of maleic / acrylic / vinyl alcohol. Said ST materials also describe in EP 193,360, including, for example, terpolymer 45/45/10 maleic / acrylic / vinyl alcohol. Another polymeric material that can be included is polyethylene glycol (PEG). The PEG can exhibit dispersing agent performance and can act as a clay dirt removal / anti-redeposition agent. Typical molecular weight scales for these purposes range from about 20 500 to about 100,000, preferably from about 1,000 to about 50,000 and most preferably from about 1,500 to about 10,000.

The dispersing agents of polyaspartate and polyglutamate, especially in conjunction with zeolite builders, can also be used. Dispersing agents such as those of tr. f < polyaspartate preferably have a molecular weight (average) of approximately 10,000.

Brightener Any optical brighteners or other brighteners or whitening agents known in the art can be incorporated into levels typically from about 0.01% to 1.2% by weight, in the detergent compositions herein. Commercial optical brighteners that may be useful in the present invention may be classified into subgroups including, but not necessarily limited to, stilbene, pyrazoline, coumarin, carboxylic acid, methynocyanins, dibenzotifen 5,5-dioxide, azole derivatives , 5- and 6-membered ring heterocycles, and various other agents. Examples of such brighteners are described in "The ak Production and Application of Fluorescent Brightening Agents," M. Zahradnik, published by John Wiley & Sons, New York (1982). Specific examples of optical brighteners that are useful in The present compositions are those identified in the patent of E.U.A. 4,790,856 issued to Wixon on December 15, 1988. These brighteners include the Verana PHORWHITE series of brighteners.

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, the 2- (4-styryril-phenyl) -2H-naphthol [1,2-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-aminocoumarin; 1, 2-bis (-benzimidazol-2-yl-ethylene; 1,3-diphenylpyrazolines; 2,5-bis (benzoxazol-2-yl) thiophene; 2-styryl-naphthyl- [1,2-s] oxazole; and 2- (stilben-4-yl) -2H-naphtho- [1,2-d] triazole See also U.S. Patent No. 3,646,015, issued February 29, 1972 to Hamilton.

Dye transfer inhibiting agents The compositions according to the present invention can also include one or more effective materials to inhibit the transfer of dyes from one fabric to another during the cleaning process. Generally, said 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 about 5%, and most preferably from about 0.05% to about 2%. Very 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 group N-O can be attached to both units; A is one of the following structures: -NC (O) -, -0 (0) 0-, -S-, -O-, -N =; x is O or 1; Y R is aliphatic, aliphatic, ethoxylated, 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 these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, midazole, pyrroline, piperidine and derivatives thereof.

The group N-O may be represented by the following general structures: / O O (R <) - N- (R2) y; = N- (R1) X (R3) z wherein R-j, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic or combinations thereof; x, y and z are O or 1; and the nitrogen of the N-O group can be attached or forms part of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides has a pKa < 10, preferably pKa < 7, very preferably pKa < 6. Any polymer base structure can be used as long as the amine oxide polymer formed is soluble in water and has dye transfer inhibiting properties. Examples of suitable polymeric base structures are polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers wherein one type of monomer is an amine N-oxide and the other type of ^ F monomer is an N-oxide. The amine N-oxide polymers typically have an amine to amine N-oxide ratio of 10: 1 to 1: 1,000,000. However, the number of amine oxide 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 molecular weight The average is within the range of 500 to 1,000,000; very preferred from 1,000 to 500,000; even 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 having an average molecular weight of about 50,000 and a ratio of amine to amine N-oxide of approximately 1: 4. Polymer copolymers of N-vinylporrolidone and N-C vinylimidazole (also known as "PVPVI") are also preferred for use herein. Preferably, the PVPVI has an average molecular weight in the range of 5,000 to 1,000,000, most preferably 5,000 to 200,000 and most preferably even 10,000 to 20,000. (The average molecular weight scale is determined by light scattering as described in Barth, and others, 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, preferably from 0.8: 1 to 0.3: 1, most preferably from 0.6: 1 to 0.4: 1. These copolymers can be already 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 most preferably still from about 5,000 to about 50,000 The PVP's are known to those skilled in the field of detergents; 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") that 'has an average molecular weight of around 500 to about 100,000, preferably about 1, 000 to approximately 10,000. Preferably, the ratio of PEG to PVP on ?? a ppm base stocked in wash solutions is from about 2: 1 to about 50: 1, and most preferably from about 3: 1 to about 10: 1. The detergent compositions herein may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners that also provide a dye transfer inhibiting action. If used, the compositions herein will preferably comprise from about 0.01% to 1% by weight of said optical brighteners. The hydrophilic optical brighteners useful in the present invention are those having the structural formula: Wherein R is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholine, chlorine and amino; and M is a salt-forming cation such as sodium or potassium. When in the above formula, R1 is anilino, R2 is N-2-bis-15-hydroxyethyl and M is a cation such as sodium, the brightener is acid ^^ '. bis ^ -anilino-e-ÍN ^ -bis-hidroxieti -s-triazin ^ -i amino] ^^' - stilbendisulfonic and disodium salt. This particular brightener species is commercially sold under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the hydrophilic optical brightener Preferred in the compositions herein. When in the above formula R- \ is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is the disodium salt of 4,4'-bis [( 4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonyl. This particular brightener species is marketed under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation. When in the above formula Ri is anilino, R2 is morphino and M is a cation such as sodium, the brightener is the sodium salt of acid 4,4'-bs [(4-aniol-6-) morpholino-s-triazn-2-yl) amino] 2,2'-stilbenesulfonyl. This particular brightener species is sold commercially under the Tinopal AMS-GX brand by Ciba-Geigy Corporation. The specific optical brightener species selected for use in the present invention provides especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents described above. The combination of said selected polymeric materials (e.g., PVNO and / or PVPVI) with said selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and / or Tinopal AMS-GX) provides significant dye transfer inhibition. better in aqueous washing solutions than either of those two components of detergent composition when used alone. Without being limited to the theory, it is believed that such brighteners work in this way because they have high affinity for fabrics in the wash solution and therefore they deposit relatively quickly on these fabrics. The degree to which the brighteners are deposited on the fabrics in the wash solution can be defined by a parameter called "exhaustion coefficient". The depletion coefficient is in general the ratio of a) the polishing material deposited on the cloth to b) the initial polish concentration in the wash liquor. The brighteners with coefficients J? * ^ 'F of relatively high exhaustion are best suited to inhibit the dye transfer in the context of the present invention. Of course, it will be appreciated that other types of conventional optical brightener compounds may optionally be present in the compositions herein to provide conventional "brightness" benefits to the fabrics, rather than a true dye transfer inhibiting effect. Said use is conventional and well known for detergent formulations.

Guelating agents The detergent compositions herein can also be Optionally contain one or more iron and / or manganese chelating agents. Said chelating agents can be selected from the group C consisting of aminocarboxylates, aminophosphates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, all as defined below. Without pretending to be limited by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from the washing solutions through the formation of soluble chelates.

Aminocarboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylenediaminetriacetates, nitrilotriacetates, f-ethylenediamonotetraproprionates, triethylenetetraaminohexacetates, diethylenetriaminepentaacetates and ethanoldiglicins, alkali metal, ammonium and substituted ammonium salts thereof and mixtures thereof. Aminophosphonates are also useful for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are allowed in detergent compositions and include ethylene diamine tetrakis (methylene phosphonates) as DEQUEST. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. Polyfunctionally substituted aromatic chelating agents are also useful in the compositions herein. See the patent of E.U.A. 3,812,044 issued May 21, 1974 to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene. A preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the 20 [S, S] isomer as described in the U.S.A. 4,704,223 issued November 3, 1987 to Hartman and Perkins. The compositions herein may also contain water-soluble salts (or acid form) of methyl glycine diacetic acid (MGDA) as a useful chelator or co-builder with, for example, insoluble builders such as zeolites, layered silicates and Similar. (d) If they are used, these chelating agents should generally comprise from about 0.1% to about 15% by weight of the detergent compositions herein. Most preferably, if used, the chelating agents should comprise from about 0.1% to about 3.0% by weight of said compositions.

Foam suppressants Compounds for reducing or suppressing foaming can be incorporated into the compositions of the present invention. The suppression of foam may be of particular importance in so-called "high concentration cleaning procedures" such as those described in E.U.A. 4,489,455 and 4,489,574, and in front-loading European-style washing machines. A wide variety of materials can be used as foam suppressors, and foam suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, 3a. Edition, Volume 7, pages. 430-447 (John Wiley &Sons, Inc., 1979). A category of foam suppressant of particular interest includes monocarboxylic fatty acids and soluble salts thereto. See the patent of E.U.A. 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids and salts thereof used as a suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium and lithium, as well as ammonium and alkanolammonium salts. The detergent compositions herein may also contain suds suppressants which are not surfactants. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (eg, fatty acid triglycerides), fatty acid esters of monovalent alcohols, C 8 -C 40 aliphatic ketones (eg, stearone) , etc. Other foam inhibitors include N-alkylated aminotriazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiaminoclorotriazines formed as cyanuric chloride products with two or three moles of a primary or secondary amine containing from 1 to 24 carbon atoms. , propylene oxide and monostearyl phosphates such as monostearyl alcohol phosphate ester and alkali metal diphosphates (e.g., K, Na and L!) Monostearyl and ester phosphates. Hydrocarbons constitute a preferred category of foam suppressants for detergent compositions. The hydrocarbon foam suppressors are described, for example, in U.S. Patent No. 4,265,779, issued May 5, 1981 to Gandolfo et al. The hydrocarbons, therefore, include saturated or unsaturated aliphatic, alicyclic, aromatic and heterocyclic unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin" as used in the discussion of suds suppressors, is intended to include mixtures of true paraffins and cyclic hydrocarbons. (ß Another preferred category of foam suppressors that are not Surfactants comprise silicone foam suppressors. This category includes the use of polyorganosiloxane oils such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemoabsorbed or fused in the silica. Silicone foam suppressors are well known in the art and are described, for example, in the US patent. 4,265,779, issued May 5, 1981 to Gandolfo et al. And in European patent application No. 89307851, published on February 7, 1990 by Starch, M.S. Other silicone foam suppressors are described in U.S. Patent 3,455,839, which relates to compositions and processes for the removal of foam from aqueous solutions incorporating the C same small amounts of polydimethylsiloxane fluids. Mixtures of silicone and silanated silica are described, for example, in German patent application DOS 2,124,526. Silicone foam scavengers and foam control agents in granular detergent compositions are described in US Patent 3,933,672, Bartolotta et al., And in US Patent 4,652,392, Baginski et al., Issued March 24, 1987. illustrative silicone-based foam suppressant to be used in the present is a foam suppressant amount of an agent foam controller consisting essentially of: (i) polydimethylsiloxane fluid having a viscosity of from about 20 cs to about 1, 500 cs at 25 ° C; (ii) about 5 to about 50 parts per 100 parts by weight of (i) siloxane resin composed of (CH3) 3SiO? / 2 units of units of SIO2 in a ratio of units of (CH 3) 3 SiO 2 to units of S 0 2 of about 0.6: 1 to about 1.2: 1; and (iii) about 1 to about 20 parts per 100 parts by weight of (i) of a solid silica gel. In the preferred silicone foam suppressant used in the In this case, the solvent for a continuous phase is made of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures of J ^, the same (preferred), or polypropylene glycol. The primary silicone foam suppressor is branched / interlaced and preferably non-linear. To further illustrate this point, the compositions Typical laundry detergents with controlled foaming optionally will comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5 weight percent of said silicone foam suppressant, comprising (1) ) a non-aqueous emulsion of a primary foam antifoaming agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone compound if silicone resin producer, (c) a finely divided filler material and (d) a catalyst to promote the reaction of mixture components (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. See also patents of E.U.A. 4,978,471, Starch, issued December 18, 1990 and 4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et al., Issued February 22, 1994 and patents of E.U.A. 4,639,489 and 4,749,740, Aizawa et al. In column 1, row 46 to column 4, line 35. The silicone foam suppressant herein preferably comprises polyethylene glycol and a polyethylene glycol / polypropylene glycol copolymer, all having an average molecular weight of less than about C 1, 000, preferably between about 100 and 800. The polyethylene glycol and polyethylene / polypropylene copolymers of the present have a solubility in water at room temperature other 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, most preferably between about 100 and 800, most preferably still between 200 and 400, and a polyethylene glycol / polypropylene glycol copolymer, preferably PPG 200 / PEG 300. A weight ratio of (M about 1: 1 and 1:10, most preferably between 1: 3 and 1: 6, of polyethylene glycol Polyethylene-polypropylene glycol polymer. Preferred silicone foam suppressors and used herein do not contain polypropylene glycol, particularly of molecular weight of 4,000. Preferably, they also do not contain block copolymers of ethylene oxide and propylene oxide, such as PLURONIC L101. Other foam suppressants useful herein contain the secondary alcohols (e.g., 2-alkylalkanols) and mixtures of said alcohols with silicone oils; such as the silicones described in E.U.A 4,798,679, 4,075.1 18 and EP 150,872. Secondary alcohols include Ce-Cie alkyl alcohols having a C? -C6 chain.

Preferred is 2-butyloctanol, which is available from Condea under the trade name ISOFOL 12. Mixtures of secondary alcohols are available under the tradename ISALCHEM 123 from Enichem. Mixed foam suppressors typically comprise alcohol + silicone blends at a weight ratio of 1: 5 to 5: 1. For any detergent compositions to be used in automatic washing machines, the foam should not be formed to the extent that they overflow from 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 formulator of the composition can select an amount of this foam controlling agent that will sufficiently control the foam to, result in a low foaming laundry detergent for used in automatic washing machines. The compositions herein will generally comprise from 0% to about 10% foam suppressant. When used as suds suppressors, the monocarboxylic fatty acids, and salts thereof, will typically be present in amounts of up to about 5%, by weight, of the detergent composition. Preferably, about 0.5% to about 3% of fatty monocarboxylate foam suppressant is used. Silicone foam suppressors are typically used in amounts up to about 2.0%, by weight, of the detergent composition, although amounts can be used superiors This upper limit is practical in nature, mainly due to the interest of keeping costs reduced to a minimum and the effectiveness of lower quantities to effectively control foaming. Preferably about 0.01% to about 1% silicone foam suppressant is used, most preferably from about 0.25% to about 0.5%. As used herein, these values in percent by weight include any silica that can be used in combination with polyorganosiloxane, as well as any auxiliary materials that can 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 (eg ranging from about 0.01% to about 5.0%, although can use higher levels. The alcohol foam suppressors are typically used at 0.2% -3% by weight of the finished compositions.

Alkoxylated polycarboxylates Alkoxylated polycarboxylates such as those prepared from polyacrylates are useful herein to provide additional fat removal performance. Such materials are described in WO 91/08281 and PCT 90/01815, p. 4 et seq., Incorporated herein by way of reference. Chemically, these materials comprise polyacrylates having an ethoxy side chain for every 7-8 acrylate units. The chains laterals have the formula - (CH2CH2?) M (CH2) nCH3 where m is 2-3 and n is 6-12. The side chains are attached by ester to the "structure of - » "base" of the polyacrylate to provide a "comb" type polymer structure The molecular weight may vary, but is typically in the range of from about 2000 to about 50,000 such alkoxylated polycarboxylates may comprise from about 0.05% to about 10% by weight of the compositions herein.

Fabric Softeners Various fabric softeners that soften during washing, especially the impalpable smectite clays of the U.S. Patent may optionally be used. 4,062,647, Storm and Nirschi, issued on December 13, 1977, as well as other softening clays known in the art, typically at levels of from about 0.5% to about 10% by weight in the compositions herein to provide softening benefits concurrently with fabric cleaning. Clay-based softeners can be used in combination with amine softeners and cationic as described, for example, in the patent of E.U.A. 4,375,416, Crisp et al., March 1, 1983 and in the patent of E.U.A. 4,291, 071, Harris et al., Issued September 22, 1981.

Perfumes 15 Perfume and perfumery ingredients useful in the present compositions and methods comprise a wide variety of natural and synthetic chemical ingredients, including, but not limited to, aldehydes, ketones, esters and the like. Also included are various natural extracts and essences that may comprise complex mixtures of ingredients such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar and the like. The finished perfumes can comprise extremely complex mixtures of said ingredients. The finished products typically comprise from about 0.01% to about 2% by weight of the detergent compositions herein, and the individual perfumery ingredients can comprise (jl 'about 0.0001% to about 90% of a composition of finished perfume. Various perfume formulations are set forth in Example XXI below. Non-limiting examples of perfume ingredients useful herein include: 7-acetyl-1,2, 3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene, methyl ionone; ionone gamma methyl; methylredrilone; 10-methyldihydrojasmonate; methyl-1, 6, 10-trimethyl-2,5,9-cyclododecatrien-1-yl ketone; 7-acetyl-1,1, 3,4,4,6-hexamethyltetralin; 4-acetyl-6-tert-butyl-1,1-dimethylindane; para-hydroxy-phenyl-butanone; benzophenone; methylbeta-naphthyl ketone; 6-acetyl-1,1, 2,3,3,5-hexamethylindane; 5-acetyl-3-isopropyl-1,1,6-tetramethylindane; 1 - dodecanal; 4- (4-hydroxy-4-methylpentyl) -3-cyclohexen-1-carboxaldehyde; 7- 15 hydroxy-3,7-d-methyloctanal; 10-undecen-1-al; iso-hexylcyclohexenylcarboxaldehyde; formyltriciclodecane; .products of C condensation of hydroxycitronellal and methyl anthranilate; condensation products of hydroxy-citronellal and indole; condensation products of phenylacetaldehyde and indole; 2-methyl-3- (para-tert-butylphenyl) -propionaldehyde; ethylvaniline; heliotropin; hexyl cinnamic aldehyde; amylcinnamic aldehyde; 2- methyl-2- (para-ε-propylphenyl) -priopionaldehyde; coumarin; decalactone gamma; Cyclopentadecanolide; 16-hydroxy-9-hexadecenoic acid lactone; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyran; methyl ether of beta-naphthol; ambroxane; dodecahydro-3a, 6,6,9a-tetramethylnaphtho [2,1 b] furan; cedrol; 5- (2,2,3-trimethylcyclopent-3-enyl) -3-methylpentan-2-ol; 2-ethyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1 -ol; alcohol • • caryophyllenic; tricyclodecenyl propionate; tricyclodecenyl acetate; benzyl salicylate; Caryl acetate and para- (tert-butyl) cyclohexyl acetate. Particularly preferred are those perfume materials that provide the greatest improvements in odor to the finished compositions containing cellulases. These perfumes include, but are not limited to: hexylcinamic aldehyde; 2-methyl-3- (para-tert-butylphenyl) -propionaldehyde; 7-acetyl-10 1, 2,3,4, 5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene; benzyl salicylate; 7- acetyl-1, 1, 3,4,4,6-hexamethyltetralin; para- (tert-butyl) cyclohexyl acetate; methyldihydrojasmonate; methyl ether of beta-naphthol; methylbeta-naphthyl ketone; 2- methyl-2- (para-iso-propylphenyl) -priopionaldehyde; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2-benzopyran; dodecahydro-3a, 6,6,9a-15 tetramethylnaphtho [2,1 b] furan; anisaldehyde; coumarin; cedrol; vanillin; Cyclopentadecanolide; tricyclodecenyl acetate and propionate C tricyclodecenyl. < Other perfume materials include essential oils, resinoids and resins from a variety of sources including, but not limited to a: balsam from Peru, resioide de olíbano, stirax, labadand resin, nutmeg, acasia oil, benzoin resin, corianda and bleach. Other perfume chemicals include phenethyl alcohol, terpineol, linalool, 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. t ^ # Other ingredients 5 A wide variety of other useful ingredients in detergent compositions can be included in the compositions herein, including other active ingredients, vehicles, hydrotropes, processing aids, dyes or pigments, solid fillers for stick compositions, etc. If high foam formation is desired, foam boosters such as C 0 -C 16 alkanolamides can be incorporated into the compositions, typically at levels of 1% -10%. C10-C4 monoethanol and diethanolamides illustrate a typical class of such foam boosters. The use of such foam boosters with high foaming adjunct surfactants such as oxides of amine, betaines and sultaines mentioned above is also advantageous. If desired, magnesium salts and / or water-soluble calcium salts such as MgCl 2, MgSO 4, CaCl 2, CaSO and the like can be added at typically 0.1% -2% levels to provide additional foam and to improve the performance of grease removal. Various detersive ingredients employed in the present compositions can be subsequently stabilized by absorbing said ingredients on a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient is mixed with a surfactant before being absorbed into the porous substrate. During use, the detersive ingredient is released from the substrate in the aqueous wash solution, where it performs its intended detersive function. To illustrate this technique in more detail, a porous hydrophobic silica (trade name SIPERNAT D10, DeGussa) is mixed with a proteolytic enzyme solution containing 3% -5% nonionic surfactant of ethoxylated C3 alcohol. 5 (EO 7). Typically, the enzyme / surfactant solution is 2.5X the weight of the silica. The resulting powder is dispersed with agitation in silicone oil (various viscosities of silicone oil can be used in the range of 500-12,500). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this means, ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, colorants, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected" for use in detergents, including liquid laundry detergent compositions. The liquid detergent compositions may comprise 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 solubilizing surfactant, however polyols, such as those containing from 2 to 6 carbon atoms and from about 2 to 6 hydroxy groups (eg, 1,3-propanediol, ethylene glycol, glycerin and 1,2-propanediol) can also be used. The compositions may contain from 5% to 90%, typically from 10% to 50% of said vehicles. The detergent compositions herein will preferably be formulated such that during use in aqueous cleaning operations, the wash water has a pH of between about 6.5 and about 11, preferably between about 7.5 and 10.5. The liquid dishwashing product formulations preferably have a pH between about 6.8 and about 9.0. Laundry products typically have a pH of 9-11. Techniques for controlling pH at recommended levels of use include the use of pH, alkali, acid regulators, etc., and are well known to those skilled in the art.

Form of the compositions The compositions according to the invention can have C .. a variety of physical forms including granulated forms, in tablets f and liquid. The compositions are particularly so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a delivery device placed in the tub of the washing machine with the load of soiled fabrics. The average particle size of the components of the granulated compositions according to the invention should preferably be such that no more than 5% of the particles are more than 1.7 mm in diameter and no more than 5% of the particles are less than 0.15. mm in diameter. The term "average particle size" as defined in "H" and "present" is calculated by sifting a sample of the composition in a number of fractions (typically 5 fractions) on a series of Tyler sieves. The fractions of weight thus obtained are grained against the opening size of the sieves. The average particle size is considered the size of the opening through which 50% by weight of the sample would pass. The overall density of the granular detergent compositions according to the present invention is typically an overall density of at least 600 g / liter, most preferably from 650 g / liter to 1200 g / liter. The overall density is measured by means of a simple funnel and cup device consisting of a conical funnel rigidly molded on a base and provided with a butterfly valve at its lower end to allow the contents of the funnel to be emptied into an axially aligned cylindrical cup disposed below the funnel. The funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective upper and lower extremities. It is mounted in such a way that the lower extremity is 140 mm on the upper surface of the base. The cup has a total height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.

To carry out a measurement, the funnel is filled with manually poured powder, the butterfly valve is opened and the powder is allowed to overfill the cup. The full cup is removed from the frame and the excess powder (© 'is removed from the cup by passing a straight edge implement, for example, a knife, through its upper edge. The filled cup is then weighed and the value obtained for the weight of the powder is doubled to provide a global density in g / liter. Equal measurements are made as required.

Agglomerated particles of branched primary algayl surfactant in the middle region of its chain The branched primary alkyl surfactant system in the middle region of its chain is present preferably in granular compositions in the form of agglomerated particles of surfactant of branched primary alkyl in the middle region of its chain, which may be in the form of flakes, pellets, discs, noodles, ribbons, but preferably have the form of granules. The most preferred form for processing the particles is by agglomerating powders (eg, aluminosilicate, carbonate) with highly branched primary alkyl branched surfactant pastes in the middle of their chain and controlling the particle size of the resulting agglomerates within specific limits. Said process includes mixing an effective amount of powder with a primary alkyl branched surfactant paste in the middle region of its highly active chain in one or more agglomerators such as a container agglomerator, a Z-shaped paddle mixer or most preferably a in-line mixer such as those manufactured by Schugi (Netherlands) BV, 29 Chroomstraat 8211 AS, Leyland, The Netherlands, and I Gebruder Lodige Maschinebau GmbH, D-4790 Paderbom 1, Elsenerstrasse 7- 5 9, Postfach 2050, Germany. Most preferably a high shear mixer is used, such as a Lodige CB (tradename). A branched primary alkyl surfactant paste is typically used in the middle region of its highly active chain comprising from 50 wt% to 95 wt%, preferably 70 wt% to 85 wt% of branched primary alkyl surfactant in the middle region of its chain. The paste can be pumped into the agglomerator at a temperature high enough to maintain a pumpable viscosity, but low enough to avoid degradation of the surfactants used. A pulp operating temperature of 15 50 ° C to 80 ° C is typical. r, Laundry Washing Method The laundry washing methods of the present invention typically comprise treating the laundry with an aqueous washing solution in a washing machine having dissolved or supplied therein an effective amount of a washing detergent composition in the laundry. machine according to the invention. For an effective amount of the detergent composition is meant from 20 g to 300 g of product dissolved or dispersed in a washing solution of a volume of 5 to 65 liters, which are typical doses of product and in volumes of wash solution commonly used in conventional machine washing methods. I f As mentioned, the primary alkyl surfactants Branched in the middle region of its chain are used herein in detergent compositions, preferably in combination with other detersive surfactants, at levels that are effective to achieve at least a directional improvement in cleaning performance. In the context of a composition for washing fabrics, said "use levels" may vary depending not only on the type and severity of the soils and stains, but also on the temperature of the washing water, the volume of the washing water and the type of washing machine. For example, in a vertical-type, front-loading, automatic American type washing machine that uses approximately 45 to 83 liters of water in the wash bath, a wash cycle of approximately to about 14 minutes and a wash water temperature of At about 10 ° C to about 50 ° C, it is preferred to include from about 2 ppm to about 625 ppm, preferably about 2 ppm to about 550 ppm, most preferably about 10 ppm to about 235 ppm, of the branched primary alkyl surfactant in the middle region of its chain in the wash liquor. Based on usage rates of about 50 ml to about 150 ml per wash load, this results in a product (weight) concentration of the branched primary alkyl surfactant in the middle region of its chain of about 0.1% to about 40%, preferably about 0.1% to about 35%, most preferably about 0.5% to about 15%, for a heavy-duty liquid laundry detergent. Based on usage rates of around 30 g to about 950 g per wash load, for granular laundry compositions ("compact") dense (density above about 650 g / l) this translates into a concentration in product (weight) of the agent the branched primary alkyl surfactant in the middle region of its chain of about 0.1% to about 50%, preferably around 0. 1% to about 35%, most preferably from about 0.5% to about 15%. Based on usage rates of about 80 g to about 100 g per load for spray-dried granules (that is, "foamed", density below about 650 g / l), this results in a concentration in product ( weight) of the branched primary alkyl surfactant in the middle region of its chain from about 0.07% to about 35%, preferably from about 0.07 to about 25%, most preferably from about 20 from 0.35% to about 11%. For example, in a European horizontal-axis, front-loading automatic washing machine that uses approximately 8 to 15 liters of water in the wash bath, a wash cycle of about 10 to about 60 minutes and a water temperature of washing from about 30 ° C to about 95 ° C, it is preferred to include from about 3 ppm to about 14,000 ppm, preferably from f around 3 ppm to about 10,000 ppm, most preferably from about 15 ppm to about 4200 ppm, of the branched primary alkyl surfactant in the middle region of its chain in the wash liquor. Based on usage rates of about 45 ml to about 270 ml per wash load, this results in a product concentration (weight) of the primary alkyl surfactant branched in the middle region of its chain from about 0.1% to about 50%, preferably about 0.1% to / about 35%, most preferably about 0.5% to about 15%, for a heavy duty liquid laundry detergent. Based on usage rates of approximately 40 g a about 210 g per wash load, for dense ("compact") laundry compositions (density above about 650 g / l) this translates into a product (weight) concentration of the branched primary alkyl surfactant in the middle region of your chain from about 0.12% to about 53%, Preferably from about 0.12% to about 46% and most preferably from about 0.6% to about 20%. Based on usage rates of about 140 g to about 400 g per wash load, for spray-dried granules (ie, "fluffs"; density below about 650 g / l), this results in a product (weight) concentration of the branched primary alkyl surfactant in the middle region of its chain from about 0.03% to about 34%, preferably about 0.03 % to about 24%, most preferably about 0.15% to about 10%. For example, in a vertical-load, top-loading Japanese type automatic washing machine that uses approximately 26 to 52 liters of water in the wash bath, a wash cycle of about 8 to about 15 minutes and a wash water temperature from about 5 ° C to about 25 ° C, it is preferred to include from about 0.67 ppm to about 270 ppm, preferably from about 0.67 ppm to about 236 ppm, most preferably from about 3.4 ppm to about 100 ppm, of the alkyl surfactant branched primary in the middle region of its chain in the washing liquid. Based on usage rates of about 20 ml to about 30 ml per wash load, this results in a product (weight) concentration of the branched primary alkyl surfactant in the middle region of its chain of about 0.1% a about 40%, preferably about 0.1% to about 35%, most preferably about 0.5% to about 15%, for a heavy duty liquid laundry detergent. Based on usage rates of around 18 g to about 35 g per wash load, for granular laundry compositions ("compact") dense (density above about 650 g / l) this translates into a concentration in product (weight) of the agent (fll primary branched alkyl surfactant in the middle region of its chain of about 0.1% to about 50%, preferably about 0.1% to about 35%, most preferably about 0.5% to about 15%. Based on usage rates of approximately 30 g to approximately 40 g per load of spray-dried granules (ie, "foamed", density below approximately 650 g / l), this results in a product (weight) concentration of branched alkyl primary surfactant in the middle region of its chain from about 0.06% to about 44%, preferably about 0.06% to about 30%, most preferably about 0.3% to approximately 13%. As can be seen from the above, the amount of primary alkyl branched surfactant in the middle region of its chain C used in a washing machine context may vary, depending on the habits and practices of the user, the type of washing machine and the like. However, in this context, an unavailable advantage to date of the branched primary alkyl surfactants in the middle region of their chain is their ability to at least provide directional improvements in performance over a spectrum of soils and stains, even when used at relatively low levels relative to the other surfactants ( generally anionic or anionic / non-ionic mixtures) in the finished compositions. In a preferred use aspect, a device of (f supply in the washing method.) The supply device is charged with the detergent product, and is used to introduce the product directly into the tub of the washing machine before the washing cycle begins. Its volume capacity must be such that it can contain sufficient detergent product as would normally be used in the washing method. 10 Once the washing machine has been loaded with clothes, the delivery device containing the detergent product is placed inside the drum. At the beginning of the wash cycle of the washing machine, water is introduced into the tub and it rotates periodically. The design of the dispensing device should be such as to allow the dry detergent product to be contained 15 but to then allow the release of this product during the wash cycle in response to its agitation while the tub is spinning and also as a result of its contact with the water of washing. 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 will allow 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 and transient concentrations of product in the tub of the washing machine at this stage of the wash cycle. r l < The preferred delivery 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 delivery devices for use in accordance with 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, p. 41-46, also discloses especially preferred supply devices for use with granular detergent products which are of a type commonly known as the "granulette". Another delivery device that is preferred for use in accordance with the invention is described in the patent application. 15 of PCT No. W094 / 11562. Especially preferred delivery devices are described in the European patent applications Nos. 0343069 and 0343070. This latter application describes a device comprising a flexible liner in the form of a bag extending from a support ring defining a hole, the orifice being adapted to admit sufficient product into 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 then passes down through the orifice into the washing medium. The support ring is provided with a masking arrangement to prevent the exit of the moistened and undissolved product, this arrangement typically comprising radial walls extending from a ^ # central protrusion in a wheel configuration with spokes or structure similar, in which the walls have a helical shape. Alternatively, the delivery device may be a flexible container, such as a bag or sack. The bag may have a fibrous structure coated with a waterproof protective material to thereby retain the contents, such as that described in published European patent application No. 0018678. Alternatively, the bag may be formed of a polymeric material synthetic water insoluble provided with a seal or edge closure designed to break in the aqueous medium as described in published European patent applications Nos. 0011500, 0011501, 0011502 and 0011968. A convenient form of closure water impermeable comprises a water soluble adhesive disposed along and sealing one end of a bag formed of a polymeric film C waterproof such as polyethylene or polypropylene.

Packing for compositions 20 Commercially sold executions of bleaching compositions can be packaged in any suitable container including those made of paper, cardboard, plastic materials and any suitable laminates. A preferred packaging embodiment is described in European application No. 94921505.7.

LAS: Linear Sodium Alkylbenzenesulfonate of C 2 MBASX: Primary Alkylsulfate branched in the middle region of its chain (average total carbons = x) MBAE: Alkylated primary ethoxylated alkyl in the middle region of its chain (E = 9; average total aquiloal carbons) = 15) MBAE xyS ° z- Ethoxylated alkylsulfate (average EO = x) branched primary in the middle region of its chain (average total alkyl carbons = z) LMFAA: C2-C14 alkyl N-methylglucamide APA: C8-C10 Amidopropyl dimethylamine Acid Fatty: Fatty acid of C12-C14 (012/14) Fatty acid (TPK): Fatty acid of palm seed Fatty acid (RPS): Fatty acid of rapese Borax: Tetraborate of sodium decahydrate PAA: Acid poliacrlico (pm = 4500) PEG: Polyethylene glycol (pm = 4600) MES: Alkylmethyl ester sulfate SAS: Alkylsulfate secondary NaPS: Sodium paraffinsulfonate STPP: Sodium tripolyphosphate C45AS: Sodium alkyl alkylsulphate of C14-C15 CxyEzS: Sodium alkylsulfate of C x-Ciy condensed with a C * average of z moles of ethylene oxide 5 CxyEz: A branched primary alcohol of C? X-C and condensate with an average of z moles of ethylene oxide QAS: R2.N + (CH3) 2 (C2H4OH) with R2 = Cl2-Ci4 TFAA: C-alkyl N-methylglucamide -Ci8 DSDMAC: Distearyldimethylammonium Chloride 10 STPP: Anhydrous sodium tripolyphosphate Zeolite A: Hydrated sodium aluminosilicate of the formula Nai2 (A1? 2Si? 2) i2- 27H2O, which has a size of primary particle on the scale of 0.1 to 10 microns NaSKS-6: Crystalline layered silicate of the formula d-Na2Si2? 5 Carbonate: Anhydrous sodium carbonate with a particle size average between 200 μm and 900 μm Bicarbonate: Anhydrous sodium bicarbonate with a distribution of particle size between 400 μm and 1200 μm Silicate: Amorphous sodium silicate (Si? 2"Na2 ?; 2.0 ratio) Sodium sulfate: Anhydrous sodium sulfate MA / AA: 1: 4 maleic acid / acrylic acid copolymer with an average molecular weight of about 70,000 CMC: Sodium carboxymethylcellulose Methyl cellulose Shin Etsu Co. under the registered name of MTELOSE HPCM Hydroxypropyl methylcellulose HEMC Hydroxyethyl methylcellulose Protease: Proteolytic enzyme activity 4KNPU / g sold by NOVO Industries A / S under the trade name Savinase Cellulase: Cellulite enzyme activity 1000CEVU / g sold by NOVO Industries A / S under the trade name Carezyme Amylase: Amylolytic enzyme of activity 60KNU / g sold by NOVO Industries A / S under the trade name Termamyl 60T Lipase: Lipolytic enzyme activity of 100kLU / g sold by NOVO Industries A / S under the trade name Lipolase PB4: Anhydrous sodium perborate tetrahydrate of the nominal formula NaB? 2-3H2O.H2? 2 PB1: Anhydrous sodium perborate bleach of nominal formula NaB? 2-H2? 2 Percarbonate: Sodium percarbonate of nominal formula 2Na2C03.3H2? 2 NaDCC: Sodium dichloroisocyanurate NOBS: Nonanoyloxybenzenesulfonate in the form of sodium salt TAED: Tetraacetylethylenediamine DTPMP: Diethylenetriaminpenta (methylene phosphonate) marketed by Monsanto under the trade name Dequest 2060 Photoactivated bleach: Sulfonated zinc phthalocyanine encapsulated in dextrin-soluble polymer Brightener 1: 4,4'-bis (2-sulfoestyryl) biphenyl disodium Brightener 2: 4,4, -bis (4-anilino-6-morpholino-1 I3,5-triazin-2-yl) amino) ester -2,2'-d-sulphonate disodium Brightener 3: 4, 4, -bis (disodium 4-anilino-6-bis (2-hydroxyethyl) amino-1, 3,5-triazin-2-yl) amino) stilbene-2,2'-disulfonate Brightener 4 : 4,4'-b¡s ((4-anilino-6- (N-methyl-N-2-hydroxyethyl) amino-1, 3,5-triazin-2-yl) amino) stilbene-2,2 ' disodium-sodium disulfonate 5: 2- (4-styryl-3-sulfophenyl) -2H-naphtho (1,2-d) -triazole sodium ester HEDP: 1, 1-hydroxyethane-phosphonic acid SRP 1: Esters of sulfobenzoyl-blocked ends with base structure of oxyethyleneoxy and terephthaloyl Silicon Anti-Foam: Polydimethylsiloxane foam controller with a siloxane-oxyalkylene copolymer as a dispersing agent with a ratio of said foam controller to said dispersing agent from 10: 1 to 100: 1 DTPA: Diethylenetriaminpentaacetic acid In the following examples all levels are cited as% is weight of the composition. The following examples are illustrative of the present invention, but are not intended to limit or otherwise define its scope. All parts, percentages and relationships used herein are expressed as percentages by weight, unless otherwise indicated.

EXAMPLE 1 The following laundry detergent compositions A to D were prepared according to the invention: EXAMPLE 2 The following laundry detergent compositions E a They were prepared according to the invention: H MBAS (total average of 14.8 16.4 12.3 8.2 4.1 carbons = 16.5) Any combination of 4.1 8.2 12.3 C45 AS C45E1S LAS SAS of C16 NaPS of C14-17 MES of C14-18 TFAA 1.6 C24E3 4.9 4.9 4.9 4.9 4.9 Zeolite A 15 15 15 15 15 NaSKS-6 11 11 11 11 11 Citrate MA / AA 4.8 4.8 4.8 4.8 4.8 HEDP 0.5 0.5 0.5 0.5 0.5 Carbonate 8.5 8.5 8.5 8.5 8.5 Percarbonate 20.7 20.7 20.7 20.7 20.7 HPMC 3.0 3.0 10.0 0.5 1.0 TAED 4.8 4.8 4.8 4.8 4.8 Protease 0.9 0.9 0.9 0.9 0.9 Lipase 0.15 0.15 0.15 0.15 0.15 Carezyme 0.26 0.26 0.26 0.26 0.26 Amylase 0.36 0.36 0.36 0.36 0.36 SRP 0.2 0.2 0.2 0.2 0.2 ft EXAMPLE 3 The following laundry detergent compositions J to O 10 were prepared according to the invention: fifteen ft EXAMPLE 4 The following laundry detergent compositions O to R were prepared according to the invention: fifteen twenty EXAMPLE 5 The following high density detergent formulations were prepared according to the invention: (« EXAMPLE 6 The following liquid laundry detergent compositions AA to DD were prepared according to the invention: C twenty EXAMPLE 7 The following liquid detergent compositions for Vl Laundry EE to II were prepared according to the invention: fifteen EXAMPLE 8 The following laundry detergent compositions A to D ("Were prepared according to the invention: fifteen G twenty EXAMPLE 9 The following laundry detergent compositions E a? • were prepared according to the invention: C 20 fc « EXAMPLE 10 The following laundry detergent compositions J to O 10 were prepared according to the invention: C 20 EXAMPLE 11 The following laundry detergent compositions OaR prepared according to the invention: EXAMPLE 12 The following liquid laundry detergent compositions AA to DD were prepared according to the invention: EXAMPLE 13 The following liquid laundry detergent compositions EE to II were prepared according to the invention: € • fifteen ft EXAMPLE 14 The solutions of prototype formulas for laundry were plowed as shown below: PPM ingredients in the washing solution EXAMPLE 15 The following laundry detergent compositions A a repaired according to the invention: EXAMPLE 16 The following laundry detergent compositions J to N were prepared according to the invention: « EXAMPLE 17 The following laundry detergent compositions O to S 10 were prepared according to the invention: r- 20 EXAMPLE 18 The following high density detergent formulations T to V were prepared according to the invention: EXAMPLE 19 The following liquid laundry detergent compositions W to Z were prepared according to the invention: 20

Claims (7)

1. NOVELTY OF THE INVENTION
2. CLAIMS l. 5 1. A detergent composition comprising: A. at least 0. 5%, by weight of branched surfactant compounds in the middle region of its chain and longer alkyl chain of the formula: A-XB wherein: (1) AD is a branched alkyl portion in the middle region of its hydrophobic chain from C9 to C22, total carbon atoms in the portion, preferably from about C12 to about C18, which has: (a) a longer linear carbon chain attached to the -X-B portion on the 8 to 21 scale carbon atoms; (b) one or more C -C3 alkyl portions branching from its longer linear carbon chain; (c) at least one of the branched alkyl portions is attached directly to a carbon of the longest linear carbon chain at a position within the carbon scale of position 2, counting from the # 1 carbon that is attached to the -X-B- portion, at the w-carbon 2 position, the terminal carbon minus 2 carbons; and (d) the surfactant composition has a total number of 20 average carbon atoms in the A ^ -X portion in the above formula within the range of more than 14.5 to about 18, preferably more than about 14.5 to about 17.5, most preferably from about 15 to about 17; (2) B is a polyoxyethylene polyoxypropylene preferably hydrophilic portion selected from sulfates, sulfonates, amine oxides, polyoxyalkylene, alkoxylated sulfates, polyhydroxy portions, phosphate esters, glycerol sulfonates, polygluconates, esters % j polyphosphate, phosphonates, sulfosuccinates, sulfosuccinates, carboxylates 5 polyalkoxylates, glucamides, taurinates, sarcosinates, glycinates, isethionates, dialkanolamides, monoalkanolamides, monoalkanolamide sulfates, diglycolamides, diglycolamide sulfates, glycerol esters, glycerol ester sulfates, glycerol ethers, glycerol ether sulphates, polyglycerol ethers, polyglycol ether sulfates, sorbitan esters, esters from sorbitan 10 polyalkoxylated amonioalcansulfonatos, amidopropylbetaines, quats alkylated quats alkylated / polyhydroxyalkylated, quats alkylated quats alkylated / polyhydroxyalkylated oxypropyl, midazolinas, 2-yl-succinates, sulfonated alkyl esters and sulfonated fatty yacidos; and (3) X is selected from -CH2- and -
3. CO)-; and B. from about 0.001% to about 10%, by weight, of a cellulose derivative. 2.- The detergent composition in accordance with the
4. A claim 1, further characterized in that the portion AD is a branched primary alkyl portion having the formula: R R 1 R 2 R 2 CH 2 CH 2 (CH 2) w CH (CH 2) CH CH (CH 2) and CH (CH 2); where the total number of carbon atoms in the primary alkyl portion branched of this formula, including the branching R, R1 and R2, is 13 to 19; R, R1 and R2 are each independently selected from hydrogen and C1-C3 alkyl, preferably methyl, provided that R, R1 and R2 do not they are all hydrogen and, when z is 0, at least R and R1 is not hydrogen; w is an integer from 0 to 13; x is an integer from 0 to 13; and is an integer from 0 to 13; z is an integer from 0 to 13; and w + x + y + z is from 7 to 13. 3. The detergent composition according to any of claims 1 or 2, further characterized in that the portion AD is a primary branched alkyl portion having the formula selected from: or mixtures thereof; where a, b, d and e are integers, a + b is from 10 to 16, d + e is from 8 to 14 and where in addition, when a + b = 10, a is an integer from 2 to 9 and b is a whole from 1 to 8; when a + b = 11, a is an integer from 2 to 10 and b is an integer from 1 to 9; when a + b = 12, a is an integer from 2 to 11 and b is an integer from 1 to 10; when a + b = 13, a is an integer from 2 to 12 and b is an integer from 1 to 11; when a + b = 14, a is an integer from 2 to 13 and b is an integer from 1 to 12; when a + b = 15, a is an integer from 2 to 14 and b is an integer from 1 to 13; when a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to 14; when d + e = 8, d is an integer from 2 to 7 and e is an integer from 1 to 6; when d + e = 9, d is an integer from 2 to 8 and e is an integer from 1 to 7; when d + e = 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d + e = 11, d is an integer from 2 to 10 and e is an integer from 1 to 9; when d + e = 12, d is an integer from 2 to 11 and e is an integer from 1 to 10; when d + e = 13, d is an integer from 2 to j 12 and e is an integer from 1 to 11; when d + e = 14, d is an integer from 2 to 13 and e
5. 5 is an integer from 1 to 12. 4. The detergent composition according to any of claims 1 or 2, further characterized in that the cellulose derivative is a water-soluble cellulose ether derivative selected from the group consisting of derivatives of non-ionic cellulose, cellulose derivatives 10 cationics, and mixtures thereof. 5. A detergent composition comprising: A. at least 5%, by weight of branched surfactant compounds in the middle region of its chain and longer alkyl chain of the formula: A &-XB 15 wherein: (a) ) AD is a branched alkyl portion in the middle region of its hydrophobic chain of C9 to C22, total carbon atoms in the portion, preferably from about C12 to about C18, which has: (a) a longer linear carbon chain bound to the -X -B portion on the scale of 8 to 21 carbon atoms; (b) one or more alkyl portions of C -C3 20 branching off from this longer linear carbon chain; (c) at least one of the branched alkyl portions is attached directly to a carbon of the longest linear carbon chain at a position within the carbon scale of position 2, counting from carbon # 1 which is attached to the -X -B- portion, to the w-carbon 2 position, the terminal carbon minus 2 carbons; and (d) the surfactant composition has a total number of average carbon atoms in the A & -X portion in the above formula within the range of more than 14.5 to about 18, preferably more than about 14.5 to about 17.5. , most preferably from 15 to about 17; (2) B is a hydrophilic portion selected from sulfates, sulfonates, amine oxides, polyoxyalkylene, preferably polyoxyethylene and polyoxypropylene, alkoxylated sulfates, polyhydroxy portions, phosphate esters, glycerol sulfonates, polygluconates, polyphosphate esters, phosphonates, sulfosuccinates, sulfosuccinates , polyalkoxylated carboxylates, glucamides, taurinates, sarcosinates, glycinates, setionates, dialkanolamides, monoalkanolamides, rponoalkanolamide sulfates, diglycolamides, diglycolamide sulfates, glycerol esters, glycerol ester sulfates, glycerol ethers, ether sulfates 15 glycerol, polyglycerol ethers, polyglycol ether sulfates, sorbitan esters, polyalkoxylated sorbitan esters, ammonium alkanesulfonates, amidopropylbetaines, alkylated cuats, alkylated / polyhydroxyalkylated quats, alkylated cuats, alkylated / polyhydroxyalkylated oxypropyl quads, imidazolines, 2-l-sucinates, esters sulfonated alkyl and fatty acids 20 sulfonated; and (3) X is selected from -CH2- and -C (O) -; and B. of around 0. 01% to about 5%, by weight, of a cellulose derivative, selected from the group consisting of nonionic cellulose derivatives, cationic cellulose derivatives, and mixtures thereof.
6. 6. - The detergent composition according to claim 5, further characterized in that it comprises adjunct ingredients of detergent composition selected from the group consisting of fill builders, enzymes, bleaches, surfactants 5 detersives, and mixtures thereof.
7. 7. The detergent composition according to claim 5, further characterized in that the cellulose derivative is selected from the group consisting of methylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, and mixtures thereof. 10