MXPA01007838A - Low density enzyme granulates and compositions employing same - Google Patents

Abstract

This invention relates to laundry detergent products, such as heavy duty aqueous and/or non-aqueous and/or gelled liquid laundry detergents and powder laundry detergents, which include one or more enzyme granulates comprising one or more enzyme granulate density-reducing components and one or more enzymes, and optionally one or more conventional cleaning adjunct materials.

Description

LOW DENSITY ENZYME GRANULATES, AND COMPOSITIONS THAT USE THEMSELVES FIELD OF THE INVENTION This invention relates to laundry detergent products, such as laundry laundry detergents and liquid and / or non-aqueous and / or heavy duty gelled laundry detergents, which include one or more enzyme granules comprising one or more more density reducing components of enzyme granules and one or more enzymes, and optionally one or more conventional cleaning adjunct materials.

BACKGROUND OF THE INVENTION The incorporation of conventional enzymes in conventional liquid laundry detergents has been problematic due to the tendency of enzymes, typically in the form of enzyme granules, to settle and / or settle in liquid detergent products, especially during storage and / or storage. the transportation of liquid detergent products. This problem is also present, although usually not to the same degree, in granular and / or powder laundry detergents, where the enzyme granules tend to settle and / or settle in detergent powders and / or granules during storage. , transportation and / or any other activity that results in the sifting of the products. In light of the foregoing, it is clear that formulators of liquid laundry detergents comprising enzymes have found a challenge to stably suspend the enzymes in the form of granulates in liquid laundry detergents. There is a need to formulate liquid laundry detergent compositions having enzymes stably suspended in the form of enzyme granulates. There is a need to formulate powdered and / or granular laundry detergent compositions having enzymes stably suspended in the form of enzyme granulates. There is a need to provide methods for producing enzyme granulates that can be stably suspended in laundry detergent compositions. Accordingly, there is a need to identify materials and methods that can be used to suspend and / or stably incorporate enzymes in the form of enzyme granulates in laundry detergent products in powder and / or granulates and / or liquids.

BRIEF DESCRIPTION OF THE INVENTION The present invention meets the needs identified above, by providing enzyme granulates having properties such that the tendency of said enzyme granules to settle or settle in detergent products for laundry powder and / or granulates and / or liquids is reduced; Methods for manufacturing said enzyme granules, compositions comprising said enzyme granules, and products comprising said enzyme granules are also provided. Surprisingly, it has been found that by incorporating enzyme granule density reducing components into the enzyme granulates, the enzyme granulates of the present invention can be stably suspended in laundry detergent products and / or granulates and / or liquids. . By stably suspending the enzyme granules of the present invention in laundry detergent powder and / or granular and / or liquid products, the enzyme granules of the present invention exhibit a reduced tendency to settle and / or settle into detergent products for laundry during storage and / or transportation. As a result of enzyme granulates exhibiting a reduced tendency to settle and / or settle into laundry detergent products, consumers may have doses more consistent with respect to the level of active agents, especially enzyme granulates, per dose. In one aspect of the present invention, an enzyme granulate comprising a density-reducing component of the enzyme granulate is provided. In another aspect of the present invention, a powder and / or granular and / or liquid laundry detergent composition comprising the enzyme granulate of the present invention is provided. In yet another aspect of the present invention, a laundry detergent powder and / or granular and / or liquid product comprising the enzyme granulate of the present invention is provided. In still another aspect of the present invention, there is provided a method for producing the enzyme granulate of the present invention. In yet another aspect of the present invention, a method for washing fabrics is provided, which comprises contacting the fabrics with the enzyme granulate of the present invention, preferably a laundry detergent powder and / or granulate and / or liquid comprising the enzyme granulate of the present invention. It is an object of the present invention to formulate enzyme granules having properties such that the tendency of said enzyme granules to settle or settle in detergent products for laundry powder and / or granules and / or liquids is reduced.

These and other aspects, objectives, features and advantages will be apparent from the detailed description, the examples and the appended claims. All percentages, ratios and proportions herein are on a weight basis, unless otherwise indicated. All documents cited herein are incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to enzyme granulates comprising density-reducing components of enzyme granulates, which reduce the tendency of said enzyme granules to settle and / or settle into powder and / or granular and / or liquid laundry detergent compositions. . "Enzyme granulation", as used herein, means that it encompasses any solid form in which one or more enzymes are physically and / or chemically incorporated. Typically, the enzyme granulates are free-flowing, low-dust granules with a diameter between about 200 and 1000 μm. Said enzyme granulates can be formed by any suitable granulation process. For example, the enzyme granulate can be a T-granulate, such as the T-granules obtained by the process described in the U.S. Patents. Nos. 4,106,991, 4,661, 452 and 4,876,198, all to Novo Nordisk A / S: a granulate obtained by a pelletizing or cooling-spraying process, as described by HA Herrmann, I. Good, A. Láufer in Surfactant Science Series, Vol. 69, Enzymes in Detergency, Marcel Dekker, Inc., New York, 1997, p. 281-286, 314; a granulate obtained by an extrusion process and optionally spheronization, such as the MOM process as described in the patent of E.U.A. No. 4,242,219 to Gist-Brocades, patent of E.U.A. No. 4,661, 452 to Novo Nordisk A / S, Great Britain Patent No. 1 362 365 and / or as described by HA Herrmann, I. Good, A. Laufer in Surfactant Science Series, Vol. 69, Enzymes in Detergency , Marcel Dekker, Inc., New York, 1997, p. 286-287, 314-315; a granulate obtained by a fluidized bed spray coating process, as described in the patent of E.U.A. No. 4,689,297 to Miles Laboratories, patent of E.U.A. No. 5,324,649 to Genencor International and / or by H. A. Herrmann, I. Good, A. Lauffer in Surfactant Science Series, Vol. 69, Enzymes in Detergency, Marcel Dekker, Inc., New York, 1997, pp. 287-293, 316-318; or a granulate obtained by the rapid mixer method as described by H. A. Herrmann, I. Good, A. Laufer in Suryactant Science Series, Vol. 69, Enzymes in Detergency, Marcel Dekker, Inc., New York, 1997, p. 280-281. "Enzyme granulate density reducing components", mean in the present any component that when incorporated into the enzyme granulate, results in the enzyme granulate having a reduced density, compared to the density of the enzyme granulate before the incorporation of the density reducing components of the enzyme granulate. Suitable examples of density-reducing components of the enzyme granulate include, but are not limited to, microspheres (containing liquid hydrocarbon and / or containing gas, depending on temperature, and / or hollow microspheres), cavities, pores, and others. components that result in a reduction of the density of an enzyme granulate, comparatively with the density of an enzyme granulate before the incorporation of the components.

Enzyme granulate The enzyme granulate of the present invention comprises: (a) one or more density reducing components of the enzyme granulate of the present invention; and (b) one or more enzymes.

DENSITY REDUCING COMPONENTS OF THE ENZYME GRAIN Preferably, the density reducing components of the enzyme granulate are selected from the group consisting of: microspheres, components that form cavities, components that form pores, and mixtures thereof. More preferably, the density reducing component of the enzyme granulate is selected from the group consisting of microspheres, preferably liquid and / or gas containing hydrocarbon containing microspheres, more preferably liquid hydrocarbon containing microspheres, made from one or more selected materials of the group consisting of: plastics, proteins, siliceous materials, ceramics, and mixtures thereof. The plastic microspheres of the present invention are made of one or more plastics selected from the group consisting of: thermoplastics, acrylonitrile; methacrylonitrile; polyacrylonitrile; polymethacrylonitrile; and mixtures thereof. The siliceous microspheres of the present invention are preferably made from one or more siliceous materials selected from the group consisting of glass. It is desirable that the microspheres of the present invention be able to expand, so as to increase the volume of the microspheres. It is even more desirable that the microspheres of the present invention be made of a material such that the density of the expanded microspheres is less than about 0.4 g / ml, more preferably less than about 0.2 g / ml, most preferably less than about 0.1 g / ml. To facilitate the expansion of the microspheres, it is desirable that the microspheres contain a suitable blowing agent. The blowing agent may be selected from the group consisting of liquid hydrocarbons, gases, and mixtures thereof. Suitable liquid hydrocarbons are liquid hydrocarbons that are vaporizable at a temperature lower than the softening point of the microsphere material. Examples include, but are not limited to, propane, propylene, butene, n-butane, isobutane, isopentane, neopentane, n-pentane, hexane, heptane, petroleum ether, halogenated methane, tetraalkylsilane, and the like. In addition to the liquid hydrocarbons, which may be in the form of a gas depending on temperature, the blowing agents may also be selected from the group consisting of nitrogen, carbon dioxide, oxygen, and mixtures thereof. Preferably, the blowing agent is sobutane. Commercially available microspheres are available from Expancel of Sweden (an Akzo Nobel company) under the trademark EXPANCEL®; PQ Corp. under the trademarks PM 6545, PM 6550, PM 7220, PM 7228, EXTENDOSPHERES®, LUXSIL®, QCEL®, SPHERICEL®; and Malinckrodt, under the trademark ALBUMEX®. The enzyme granules of the present invention preferably have a particle density of from about 0.8 to about 2.1 g / ml, more preferably from about 0.8 to about 1.5 g / ml, most preferably from about 0.9 to about 1.2. g / ml.

Enzymes With respect to the enzymes in the enzyme granulate of the present invention, any suitable enzyme can be used. Preferred enzymes for use in the enzyme granulates of the present invention are selected from proteases, amylases, cellulases, and mixtures thereof. Non-limiting examples of other suitable enzymes include the following: Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases , lipoxygenases, ligninases, pullulanases, tanases, pentosanas, malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, mannanases, more preferably enzymes that degrade the plant cell wall and enzymes that do not degrade the plant cell wall (see WO 98 / 39403 A) and may include, more specifically, pectinase (see WO 98/06808 A, JP10088472 A, JP10088485 A); pectolyase (see WO98 / 06805 A1); pectin lyases free of other pectic enzymes (see WO9806807 A1); chondroitinase (see EP 747,469 A); xylanase (see EP 709,452 A, WO 98/39404 A, WO98 / 39402 A) including those derived from Microtetraspora flexuosa (see US 5683911); isopeptidase (see WO 98/16604 A); keratinase (see EP 747,470 A, WO 98/40473 A); lipase (see GB 2,297,979 A, WO 96/16153 A, WO 96/12004 A, EP 698,659 A, WO 96/16154 A); cellulase or endoglucanase (see GB 2,294,269 A; WO 96/27649 A; GB 2,303,147 A; WO98 / 03640 A; see also neutral or alkaline cellulases derived from strain VKM F-3500D from Chrysosporium lucknowense as described in W09815633 A ); polygalacturonase (see WO 98/06809 A); mycodextranase (see WO 98/13457 A); termitase (see WO 96/28558 A); cholesterol esterase (see WO 98 28394 A); or any combination thereof; and amylases; known oxidoreductases and oxidases, or combination systems including them (see DE 19523389 A1); mutant blue copper oxidases (see WO9709431 A1), peroxidases (see, for example, US 5,605,832, WO97 / 31090 A1), mannanases (see W09711164 A1); laccases, see documents W09838287 A1 or W09838286 A1 or, for example, those laccase variants having amino acid changes in Myceliophthora or Scytalidium laccases, as described in W09827197 A1, or laccase-mediated systems as described in the document DE19612193 A1), or those derived from the Coprinus strains (see, for example, WO9810060 A1 or WO9827198 A1), phenol oxidase or polyphenol oxidase (see JP10174583 A) or phenol oxidase-mediated systems (see document W09711217 A); Enhanced phenol oxidase systems (see WO 9725468 A, W09725469 A); phenol oxidases fused to an amino acid sequence having a cellulose binding domain (see WO9740127 A1, WO9740229 A1) or other phenol oxidases (see WO9708325 A, W09728257 A1) or superoxide dismutases. Oxidoreductases and / or their associated antibodies can be used, for example, with H2O2, as described in WO 98/07816 A. Depending on the type of detergent composition, other active redox enzymes can be used including, for example, for catalases (see, for example, JP09316490 A). Also useful herein are oxygenases of extracellular origin, especially fungal oxygenases such as dioxygenase of extracellular origin. The latter is more especially quercetinase, catecholase or an anthocyanase, optionally in combination with other suitable oxidases, peroxidases or hydrolytic enzymes, as described in WO9828400 A2. Examples of said suitable enzymes and / or levels of use are described in the patents of US Pat., 705,464, 5,710,115, 5,576,282, 5,728,671 and 5,707,950. The cellulases useful in the present invention include both bacterial and fungal cellulases. Preferably, they will have an optimum pH between 5 and 12 and a specific activity above 50 CEVU / mg (Cellulose Viscosity Unit). Suitable cellulases are described in the U.S. Patents. 4,435,307, J61078384 and WO96 / 02653, which describe cellulases of fungi produced respectively by Humicola insolens, Tríchoderma, Thielavia and Sporotríchum. EP 739 982 describes cellulases isolated from new species of Bacillus. Suitable cellulases are also described in GB-A-2, 075,028, GB-A-2,095,275; DE-OS-2,247,832 and W095 / 26398.

Examples of said cellulases are ceiulases produced by a strain of Humicola insolens (Humicola grísea var. Thermoidea), particularly the DSM 1800 strain of Humicola. Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of approximately 50KDa, an isoelectric point of 5.5 and containing 415 amino acids; and a ~ 43kD endoglucanase derived from Humicola insolens, DSM 1800, exhibiting cellu- lose activity; A preferred endoglucanase component has the amino acid sequence described in WO 91/17243. Other suitable cellulases are EGl 11 from Trichoderma longibrachiatum described in WO94 / 21801 to Genencor. Particularly suitable cellulases are cellulases that have color care benefits. Examples of said cellulases are the cellulases described in European Patent Application No. 91202879.2, filed November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A / S) are especially useful. See also documents W091 / 17244 and WO91 / 21801. Other cellulases suitable for fabric care and / or cleaning properties are described in WO96 / 34092, W096 / 17994 and W095 / 24471. Peroxidase enzymes are used in combination with oxygen sources, for example, percarbonate, perborate, persulfate, hydrogen peroxide, etc., and with a phenolic substrate as a bleach intensifying molecule. They are used for "solution bleaching", that is, to avoid transfer of dyes or pigments removed from substrates during washing operations to other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase and haloperoxidase such as chloro- and bromo-peroxidase. Suitable peroxidases and detergent compositions containing peroxidase are described, for example, in the patents of E.U.A. Nos. 5,705,464, 5,710,115, 5,576,282, 5,728,671 and 5,707,950, PCT International Application WO89 / 099813, WO89 / 09813, and in European Patent Application EP No. 91202882.6, filed on November 6, 1991 and EP No. 96870013.8 filed in February 20, 1996. The laccase enzyme is also suitable. Suitable enhancers are selected from the group consisting of substituted phenoxyazine and phenoxyazine, 10-phenothiazinepropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinpropionic acid (POP) and 10-methyphenoxyazine (described in the document). WO 94/12621) and substituted syringates (substituted C3-C5 alkyl syringates) and phenols. Sodium percarbonate or perborate are preferred sources of hydrogen peroxide. Enzymatic systems can be used as bleaching agents. Hydrogen peroxide may also be present by adding an enzyme system (i.e., an enzyme and therefore a substrate) which is capable of generating hydrogen peroxide at the start or during the washing and / or rinsing process. Said enzymatic systems are described in the patent application EP 91202655.6 filed on October 9, 1991. Other preferred enzymes that can be included in the laundry compositions of the present invention include lipases. Suitable lipase enzymes for detergent use include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri, ATCC 19,154, as described in British Patent 1, 372, 034. Suitable lipases include those which show a positive immunological cross-reaction with the lipase antibody, produced by the microorganism Pseudomonas fluorescent, IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trademark. Lipasa P "Amano", hereinafter referred to as "Amano-P". Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, for example Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. Especially suitable lipases are lipases such as M1 Lipase® and Lipomax® (Gist-Brocades) and Lipolase® and Lipolase Ultra® (Novo) which have proven to be very effective when used in combination with the compositions of the present invention. Also suitable are the lipolytic enzymes described in EP 258 068, WO 92/05249 and WO 95/22615 of Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 of Unilever.

Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special type of lipase, ie lipases which do not require interfacial activation. The addition of cutinases to laundry compositions has been described, for example, in WO-A-88/09367 (Genencor); WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever). In addition to the lipases referred to above, phospholipases can be incorporated into the laundry compositions of the present invention. Non-limiting examples of suitable phospholipases include: EC 3.1.1.32 Phospholipase A1; EC 3.1.1.4 Phospholipases A2; EC 3.1.1.5 Lisofolipase; EC 3.1.4.3 Phospholipase C; EC 3.1.4.4. Phospholipase D. Commercially available phospholipases include LECITASE® from Novo Nordisk A / S from Denmark and Phospholipase A2 from Sigma. When the phospholipases are included in the compositions of the present invention, it is preferred to further include the amylases. Without intending to be limited to the theory, it is considered that the combined action of phospholipase and amylase provide substantial removal of stains, especially in stains and greasy / oily stains, rigid and with a high level of color. Preferably, the phospholipase and amylase, when present, are incorporated in the compositions of the present invention in a pure enzyme weight ratio between 4500: 1 and 1: 5, preferably between 50: 1 and 1: 1. Suitable proteases are the subtilisins which are obtained from particular strains of B. subtilis and ß. licheniformis (BPN and BPN 'of subtilisin). A suitable protease is obtained from a strain of Bacillus, which has a maximum activity across the pH range of 8-12, developed and sold as ESPERASE® from Novo Industries A / S of Denmark, hereinafter "Novo" . The preparation of this enzyme and analogous enzymes is described in GB 1, 243,784 to Novo. Proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in European Patent Application Serial No. 87 303761.8, filed on April 28, 1987 (particularly pages 17, 24 and 98), and which is referred to as in the present "Protease B", and in the European patent application 199,404, Venegas, published on October 29, 1986, which refers to a modified bacterial serine proteolytic enzyme which is referred to herein as "Protease A". The protease referred to in the present "Protease C", which is a variant of a Bacillus alkaline serine protease in which Lysine replaced arginine in position 27, tyrosine replaced valine in position 104, serine replaced asparagine in the position 123, and alanine replaced threonine at position 274. Protease C is described in EP 90915958: 4, corresponding to WO 91/06637, published May 16, 1991. Genetically modified variants, particularly Protease C also they are included in the present. A preferred protease referred to as "Protease D" is a carbonyl hydrolase such as that described in the U.S.A. No. 5,677,272 and WO95 / 10591. Also suitable is a carbonyl hydrolase variant of the protease described in WO95 / 10591, which has an amino acid sequence derived from the replacement of a plurality of amino acid residues replaced in the precursor enzyme corresponding to the +210 position in combination with one or more of the following residues: +33, +62, +67, +76, +100, +101, +103, +104, +107, +128, +129, +130, +132, +135, + 156, +158, +164, +166, +167, +170, +209, +215, +217, +218, and +222, where the numbered position corresponds to natural subtilisin of Bacillus amyloliquefaciens or equivalent amino acid residues in other carbonyl hydrolases or subtilisins, such as Bacillus lentus subtilisin (co-pending US patent application Serial No. 60 / 048,550, filed June 4, 1997 and international PCT application Serial No. PCT / IB98 / 00853). They are also suitable for the present invention, the proteases described in patent applications EP 251 446 and WO 91/06637, BLAP® protease described in WO91 / 02792 and its variants described in WO 95/23221. See also a high pH protease from Bacillus sp., NCIMB 40338, described in WO93 / 18140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & amp; amp; amp;; Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo. Other suitable proteases are described in EP 516 200 of Unilever. Particularly useful proteases are described in PCT publications: WO 95/30010; WO 95/30011; and WO 95/29979. Suitable proteases are commercially available as ESPERASE®, ALCALASE®, DURAZYM®, SAVINASE®, EVERLASE® and KANNASE®, all of Novo Nordisk A / S from Denmark, and as MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM®, all from Genencor International (formerly Gist-Brocades of the Netherlands). Preferred proteases useful herein include certain variants (see WO 96/28566 A, WO 96/28557 A, WO 96/28556 A, and WO 96/25489 A). Other particularly useful proteases are the multiply substituted protease variants comprising a substitution of an amino acid residue with another amino acid residue that occurs in nature at an amino acid residue position corresponding to position 103 of Bacillus subtilisin amyloliquefaciens in combination with a substitution of an amino acid residue with another amino acid residue occurring naturally at one or more amino acid residue positions corresponding to positions 1, 3, 4, 8, 9, 10, 12, 13, 16 , 17, 18, 19, 20, 21, 22, 24, 27, 33, 37, 38, 42, 48, 55, 57, 58, 61, 62, 68, 72, 75, 76, 77, 78, 79 , 86, 87, 89, 97, 98, 99, 101, 102, 104, 106, 107, 109, 111, 114, 116, 117, 119, 121, 123, 126, 128, 130, 131, 133, 134 , 137, 140, 141, 142, 146, 147, 158, 159, 160, 166, 167, 170, 173, 174, 177, 181, 182, 183, 184, 185, 188, 192, 194, 198, 203 , 204, 205, 206, 209, 210, 211, 212, 213, 214, 215, 216, 217 , 218, 222, 224, 227, 228, 230, 232, 236, 237, 238, 240, 242, 243, 244, 245, 246, 247, 248, 249, 251, 252, 253, 254, 255, 256 , 257, 258, 259, 260, 261, 262, 263, 265, 268, 269, 270, 271, 272, 274 and 275 of subtilisin of ßac / 7 / us amyloliquefaciens; wherein when said protease variant includes a substitution of amino acid residues at positions corresponding to positions 103 and 76, there is also a substitution of an amino acid residue at one or more amino acid residue positions that are not the amino acid residue positions. amino acid residue corresponding to positions 27, 99, 101, 104, 107, 109, 123, 128, 166, 204, 206, 210, 216, 217, 218, 222, 260, 265 or 274 of Bacillus amyloliquefaciens subtilisin and / or multiple-substituted protease variants comprising a substitution of an amino acid residue with another naturally occurring amino acid residue at one or more amino acid residue positions corresponding to positions 62, 212, 230, 232, 252 and 257 of Bacillus amyloliquefaciens subtilisin as described in PCT applications Nos. PCT / US98 / 22588, PCT / US98 / 22482 and PCT / US98 / 22486, all filed on October 23, 1998 by The Procter & Gamble Company (cases of P &G 7280 & , 7281 &7282L, respectively). More preferably, the protease variant includes a series of substitutions selected from the group consisting of: 12/76/103/104/130/222/245/261; 62/103/104/159/232/236/245/248/252; 62/103/104/159/213/232/236/245/248/252; 62/101/103/104/159/212/213/232/236/245/248/252; 68/103/104/159/232/236/245; 68/103/104/159/230/232/236/245; 68/103/104/159/209/232/236/245; 68/103/104/159/232/236/245/257; 68/76/103/104/159/213/232/236/245/260; 68/103/104/159/213/232/236/245/248/252; 68/103/104/159/183/232/236/245/248/252; 68/103/104/159/185/232/236/245/248/252; 68/103/104/159/185/210/232/236/245/248/252; 68/103/104/159/210/232/236/245/248/252; 68/103/104/159/213/232/236/245; 98/103/104/159/232/236/245/248/252; 98/102/103/104/159/212/232/236/245/248/252; 101/103/104/159/232/236/245/248/252; 102/103/104/159/232/236/245/248/252; 103/104/159/230/236/245; 103/104/159/232/236/245/248/252; 103/104/159/217/232/236/245/248/252; 103/104/130/159/232/236/245/248/252; 103/104/131/159/232/236/245/248/252; 103/104/159/213/232/236/245/248/252; and 103/104/159/232/236/245. Even more preferably, the protease variant includes a series of substitutions selected from the group consisting of: 12R / 76D / 103A / 104T / 130T / 222S / 245R / 261 D; 62D / 103A / 1041 / 159D / 232V / 236H / 245R / 248D / 252K; 62D / 103A / 1041 / 159D / 213R / 232V / 236H / 245R / 248D / 252K; 68A / 03A / 1041 / 159D / 209W / 232V / 236H / 245R; 68A / 76D / 103A / 1041 / 159D / 213R / 232V / 236H / 245R / 260A; 68A / 103A / 1041 / 159D / 213E / 232V / 236H / 245R / 248D / 252K; 68A / 103A / 1041 / 159D / 183D / 232V / 236H / 245R / 248D / 252K; 68A / 103A / 1041 / 159D / 232V / 236H / 245R; 68A / 103A / 1041 / 159D / 230V / 232V / 236H / 245R; 68A / 103A / 1041 / 159D / 232V / 236H / 245R / 257V; 68A / 103A / 1041 / 159D / 213G / 232V / 236H / 245R / 248D / 252K; 68A / 103A / 1041 / 159D / 185D / 232V / 236H / 245R / 248D / 252K; 68A / 103A / 1041 / 159D / 185D / 210L / 232V / 236H / 245R / 248D / 252K; 68A / 103A / 1041 / 159D / 210L / 232V / 236H / 245R / 248D / 252K; 68A / 103A / 1041 / 159D / 213G / 232V / 236H / 245R; 98L / 103A 1041 / 159D / 232V / 236H / 245R / 248D / 252K; 98L / 102A / 103A 1041 / 159D / 212G / 232V / 236H / 245R / 248D / 252K; 101 G / 103A / 1041 / 159D / 232V / 236H / 245R / 248D / 252K: 102A 103A / 1041 / 59D / 232V / 236H / 245R / 248D / 252K: 103A / 1041 / 159D / 230V / 236H / 245R; 103A / 1041 / 159D / 232V / 236H / 245R / 248D / 252K; 103A / 1041 / 159D / 217E / 232V / 236H / 245R / 248D / 252K; 103A / 1041 / 130G / 159D / 232V / 236H / 245R / 248D / 252K; 103A / 1041/131 V / 159D / 232V / 236H / 245R / 248D / 252K; 103A / 1041 / 159D / 213R / 232V / 236H / 245R / 248D / 252K; and 103A / 1041 / 159D / 232V / 236H / 245R. More preferably, the protease variant includes the series of substitutions 101/103/104/159/232/236/245/248/252, preferably 101 G / 103A / 1041 / 159D / 232V / 236H / 245R / 248D / 252K . Bleach / amylase / protease combinations are also useful (see EP 755,999 A, EP 756,001 A, EP 756,000 A). Also in relation to the enzymes herein, enzymes and their directly linked inhibitors, for example, protease and its inhibitor linked by a peptide chain as described in WO 98/13483 A, are useful in conjunction with the present breeders. of hybrid detergency. Enzymes and their unbound inhibitors used in combinations selected herein, include protease with protease inhibitors selected from proteins, peptides and peptide derivatives as described in WO 98/13461 A, WO 98/13460 A, WO 98 / 13458 A and WO 98/13387 A. Amylases with amylase antibodies can be used as described in WO 98/07818 A and WO 98/07822 A, lipases can be used in conjunction with lipase antibodies as described in WO 98/07817 A and WO 98/06810 A, proteases can be used in conjunction with protease antibodies as described in WO 98/07819 A and WO 98/06811 A, cellulases can be combined with cellulase antibodies as is described in WO 98/07823 A and WO 98/07821 A. More generally, the enzymes can be combined with similar or different enzyme-directed antibodies, as described, for example, in WO 98/07820 A or WO 98/06812 A. Enzymes Preferred herein may be of any suitable origin, such as of vegetable, animal, bacterial, fungal and yeast origin. Preferred selections are influenced by factors such as stability and / or pH activity optima, thermostability and stability to activate detergents, builders, and the like. In this regard, bacterial or fungal enzymes, such as amylases and proteases of bacteria and fungal cellulases, are preferred. Amylases (a and / or ß) can be included for removal of carbohydrate-based stains. WO94 / 02597 describes laundry compositions which incorporate mutant amylases. See also WO95 / 10603. Other amylases known for use in laundry compositions include α- and β- amylases. α-amylases are known in the art and include those described in the US patent. No. 5,003,257 and in EP 252,666; WO / 91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and British Patent Specification No. 1, 296,839 (Novo). Other suitable amylases are stability enhancing amylases described in W094 / 18314 and WO96 / 05295, Genencor, and amylase variants having further modification in the immediate original enzyme available from Novo Nordisk A / S, described in WO 95/10603. Also suitable are the amylases described in EP 277 216. Examples of commercial α-amylases products are Purafect Ox Am® from Genencor and Termamyl®, Ban®, Fungamyl® and Duramyl®, all available from Novo Nordisk A / S Denmark . W095 / 26397 describes other suitable amylases: α-amylases characterized by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25 ° C to 55 ° C and at a pH value on the scale of 8 to 10, as measured by the Phadebas® α-amylase activity test. The variants of the above enzymes, described in W096 / 23873 (Novo Nordisk), are suitable. Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher level of activity are described in W095 / 35382. The enzymes mentioned above may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast. The origin can also be mesophilic or extremophilic (psychrophilic, psychrotropic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.). The purified or non-purified forms of these enzymes can be used. Currently, it is common practice to modify wild-type enzymes through genetic / protein engineering techniques in order to optimize their efficiency in performance in the detergent washing and / or fabric care compositions of the invention. For example, the variants may be designed so as to increase the compatibility of the enzyme towards commonly found ingredients of said compositions. Alternatively, the variant may be designed so that the optimum pH, chelating or bleaching stability, catalytic activity and the like, of the enzyme variant is adjusted to the particular laundry application. In particular, attention should be paid to amino acids sensitive to oxidation in the case of bleaching stability and in surface charges for compatibility of the surfactant. The isoelectric point of said enzymes can be modified by the substitution of some charged amino acids, for example, an increase in the isoelectric point can help improve the compatibility with anionic surfactants. The stability of the enzymes can be further enhanced by the creation, for example, of additional salt bonds and reinforcing the calcium binding sites to increase the chelating stability. Other suitable detergent ingredients that may be added are enzyme oxidation scavengers. Examples of said enzyme oxidation scavengers are ethoxylated tetraethylenepolyamines. A range of enzyme materials is also disclosed in WO 9307263 and WO 9307260 to Genencor International, WO 8908694, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are also described in U.S. 4,101, 457 and U.S. 4,507,219. Useful enzyme materials for liquid detergent formulations, and their incorporation into such formulations, are described in U.S. 4,261, 868.

Granulation Procedures The enzyme granulates of the present invention can be obtained by any conventional granulation process known in the art including, but not limited to, fluid bed coating / agglomeration; mechanical agglomeration; extrusion; spray drying, etc. In addition, the density reducing components of the enzyme granulate of the present invention can be incorporated into the enzyme granulates herein at any step in the granulation process. A preferred granulation process is the granulation process T, an example of which is described in the U.S. Patents. Nos. 4,106,991, 4,661, 452 and 4,876,198, all to Novo Nordisk A / S. The granulation process T consists of (1) an agglomerator, preferably a "ploughshare" type mixer or Schugi type mixer with horizontal or vertical arrows, equipped with mixers, wherein fibrous cellulose is agglomerated with enzymes; and optionally, (2) a machine for applying top spray fluid bed coating, wherein the enzyme granulate produced in step (1) is coated with protective coatings, such as PEG 4000, Ti02 and sodium thiosulfate.

The density reducing components of the enzyme granulate of the present invention can be incorporated into the enzyme granules during the agglomeration step or the coating step of the T granulation process, preferably the agglomeration step. Another preferred granulation process is the fluidized bed top spray coating method, an example of which is described in the U.S.A. No. 5,324,649 to Genencor International. The fluidized bed top spray coating process consists of suspending one or more sugar particles (300-500 μm) in the machine to apply coating with the use of air, and then coating the sugar particles with several layers of materials, such as a starch / sugar layer, an enzyme solution layer, another starch / sugar layer and a polymer layer. The enzyme granule density reducing components can be incorporated into the enzyme granules at any step and in any layer in this process.

Laundry compositions The laundry compositions of the present invention also comprise, in addition to one or more enzyme granules of the present invention described above, one or more cleaning adjunct materials, preferably compatible with the enzymes in the enzyme granulates. The term "cleaning attachment materials", as used herein, means any liquid, solid or gaseous material selected for the particular type of laundry composition desired and the product form (e.g., liquid, granule, powder, composition in gel), whose materials are also preferably compatible with the enzymes in the enzyme granules of the present invention. The granulated compositions may also be in "compact" form and the liquid compositions may also be in "concentrated" form. The specific selection of cleaning attachment materials is easily achieved by considering the surface, the article or the fabric to be cleaned, as well as the desired shape of the composition for washing conditions during use (for example, by the use of the detergent for washing). The term "compatible", as used herein, means that the adjunct cleaning materials do not reduce the enzymatic activity of the enzymes in the enzyme granules to the extent that the enzymes are not effective as desired during the use situations. normal. Examples of suitable cleaning adjunct materials include, but are not limited to, surfactants, detergency builders, bleaches, bleach activators, bleach catalysts, other enzymes, enzyme stabilization systems, chelators, optical brighteners, dirt release polymers, dye transfer agents, dispersants, foam suppressors, dyes, perfumes, filler salts, hydrotropes, photoactivators, fluorescers, fabric conditioners, hydrolysable surfactants, preservatives, antioxidants, anticaking agents, anti-wrinkle agents, germicides, fungicides, agents against the formation of colored specks, agents for the care of silverware, anti-rust and / or anti-corrosion agents, alkalinity sources, solubilization agents, vehicles , processing aids, pigments and agents for pH control, as described in the US patents Nos. 5,705,464, 5,710,115, 5,698,504, 5,695,679, 5,686,014 and 5,646,101. Specific cleaning attachment materials are exemplified in more detail later. If the cleaning adjunct materials are not compatible with the enzymes in the enzyme granules within the cleaning compositions, then suitable methods can be used to keep the cleaning adjuncts and the enzymes separate in the enzyme granules (not in contact). between each other), until the combination of the two components is appropriate. Suitable methods can be any method known in the art, such as gel capsules, encapsulation, tablets, physical separation, etc. Preferably, an effective amount of one or more enzyme granules described above is included in the compositions useful for washing a variety of fabrics that need cleaning. As used herein, "effective amount of one or more enzyme granulates", refers to the amount of the enzyme granulate of the present invention described above, necessary to achieve the necessary enzymatic activity in the specific cleaning composition. Said effective amounts are easily ascertained by the person skilled in the art, and are based on many factors, such as the particular enzyme used, the laundry application, the specific composition of the laundry composition, and whether a liquid or dry composition is required. (for example, granulated, powdered), and the like. The laundry detergent compositions of the present invention comprise: (a) an enzyme granulate according to the present invention; and (b) one or more cleaning attachment materials. Preferably, a laundry detergent composition of the present invention comprises one or more enzyme granulates of the present invention, such that the density difference between the density of the laundry detergent composition and the density of the enzyme granules, less than about 0.2 g / ml, more preferably less than about 0.1 g / ml, most preferably less than about 0.05 g / ml. Preferably, the laundry compositions comprise about 0.0001%, preferably about 0.001%, more preferably about 0.01% by weight of the laundry compositions, of one or more enzyme granules of the present invention, up to about 10%, preferably up to about 1%, more preferably up to about 0.1%. Preferably, the enzyme granulates of the present invention comprise one or more enzymes of the present invention, such that the enzymes are present in the laundry compositions of the present invention, at a level of from about 0.0001% to about 2% , more preferably from about 0.001% to about 2%, most preferably from about 0.01% to about 1% pure enzyme, by weight of the laundry composition. Several examples of various laundry compositions in which the enzyme granules of the present invention can be used are described in more detail below. Also, laundry compositions may include from about 1% to about 99.9% by weight of the composition, of the cleaning adjunct materials. As used herein, "fabric washing compositions" include detergent compositions for machine and hand washing that include additive laundry compositions and compositions suitable for use in soaking and / or pretreatment of dyed fabrics. When formulated as compositions suitable for use in a machine laundry method, the compositions of the invention preferably contain both a surfactant and a builder, and in addition one or more detergent components that are selected. preferably of organic polymeric compounds, bleaching agents, additional enzymes, suds suppressors, dispersants, lime soap dispersants, soil suspending and anti-redeposition agents and corrosion inhibitors. The laundry compositions may also contain softening agents, as additional detergent components. The compositions of the present invention can also be used as detergent additive products in solid or liquid form. Said additive products are designed to complement or enhance the performance of conventional detergent compositions, and can be added at any stage of the washing process. If necessary, the density of the laundry detergent compositions of the present invention ranges from 400 to 1200 g / liter, preferably from 500 to 950 g / liter of the composition, measured at 20 ° C. The "compact" form of the laundry compositions of the present invention is best reflected by the density and, in terms of composition, by the amount of inorganic filler salt; the inorganic filler salts are conventional ingredients of the powder detergent compositions; in conventional detergent compositions, the filler salts are present in substantial amounts, typically 17-35% by weight of the total composition. In compact compositions, the filler salt is present in amounts not exceeding 15% of the total composition, preferably not greater than 10%, and more preferred not greater than 5% by weight of the composition. Inorganic filler salts such as those indicated in the present compositions are selected from alkali metal and alkali metal salts of sulfates and chlorides. A preferred filler salt is sodium sulfate. The liquid laundry compositions according to the present invention can also be in "concentrated form", in which case, the liquid laundry compositions in accordance with the present invention will contain a smaller amount of water, as compared to conventional liquid detergents. Typically, the water content of the liquid laundry laundry composition is preferably less than 40%, more preferred less than 30%, and most preferred still less than 20% by weight of the laundry composition.

A. Liquid detergent compositions for laundry Heavy Duty Non-Aqueous Based Liquid Detergents Lined Phase Containing Surfactant The heavy-duty non-aqueous liquid detergent compositions according to the present invention are in the form of a stable suspension of substantially insoluble particulate solid material dispersed through a Structured liquid phase containing surfactant. Said detergent compositions comprise from about 49% to 99.95% by weight of the composition, of a structured liquid phase containing surfactant which is formed by combining: i) from about 1% to 80% by weight of said liquid phase, of one or more non-aqueous organic thinners; and i) from about 20% to 99% by weight of said liquid phase, of a surfactant system comprising surfactants selected from the group consisting of anionic, nonionic, cationic surfactants, and combinations thereof. The non-aqueous liquid phase containing surfactant of the non-aqueous liquid laundry detergent compositions of the present invention will generally comprise from about 52% to about 98.9% by weight of the detergent compositions herein. More preferably, this liquid phase is structured in its surfactant, and will comprise from about 55% to 98% by weight of the compositions. Most preferably, this non-aqueous liquid phase will comprise from about 55% to 70% by weight of the compositions herein. Said liquid phase containing surfactant will often have a density of about 0.6 to 1.4 g / cc, more preferably about 0.9 to 1.3 g / cc. The liquid phase of the detergent compositions herein is preferably formed from one or more non-aqueous organic diluents in which a surfactant structuring agent is mixed which is preferably a specific type of powder containing anionic surfactant. . i. Non-Aqueous Organic Diluents The major component of the liquid phase of the detergent compositions herein, comprises one or more non-aqueous organic diluents. The non-aqueous organic diluents used in this invention can be surfactants, i.e., non-aqueous surfactant or non-surfactant liquids referred to herein as non-aqueous solvents. The term "solvent" is used herein to denote the non-aqueous, non-surfactant liquid portion of the compositions herein. Although some of the essential and / or optimum components of the compositions herein can actually be dissolved in the liquid phase containing "solvent", other components will be present as a particulate material dispersed within the liquid phase containing "solvent". Thus, the term "solvent" does not mean that it requires that the solvent material be capable of actually dissolving all the components of the detergent composition added thereto. . The non-aqueous liquid diluent component will generally comprise from about 50% to 100%, more preferably from about 50% to 80%, most preferably from about 55% to 75%, of a structured liquid phase containing surfactant. Preferably, the liquid phase of the compositions herein, i.e., the non-aqueous liquid diluent component, will comprise non-aqueous liquid surfactants and non-aqueous non-surfactant solvents.

I. Non-Aqueous Liquid Surfactants Suitable types of non-aqueous liquid surfactants that can be used to form the liquid phase of the compositions herein include alkoxylated alcohols, block polymers of ethylene oxide (EO) -propylene oxide (PO) , polyhydroxy fatty acid amides, alkylpoiisaccharides, and the like. Such normally liquid surfactants are those having a hydrophilic-lipophilic balance ranging from 10 to 16. The most preferred liquid surfactants are non-ionic alkoxylate alcohol surfactants. Alcohol alkoxylates are materials corresponding to the general formula: R1 (CmH2mO) nOH wherein R is an alkyl group of CQ-C ^ Q, m is from 2 to 4, and n varies from about 2 to 12. Preferably, R1 is an alkyl group, which may be primary or secondary, containing from about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms. Preferably also, the alkoxylated fatty alcohols will be ethoxylated materials containing from about 2 to 12 portions of ethylene oxide per molecule, more preferably from about 3 to 10 portions of ethylene oxide per molecule. The alkoxylated fatty alcohol materials useful in the liquid phase will often have a hydrophilic-lipophilic balance (HLB) ranging from about 3 to 17. More preferably, the HLB of this material will vary from about 6 to 15, more preferably from Examples of fatty alcohol alkoxylates useful in or as the non-aqueous liquid phase of the compositions herein, will include those which are formed from alcohols of 12 to 15 carbon atoms, and which contain about moles of ethylene oxide. Such materials have been marketed under the trademarks of Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company. Other useful Neodoles include Neodol 1-5, an ethoxylated fatty alcohol that averages 11 carbon atoms in its alkyl chain with about 5 moles of ethylene oxide; Neodol 23-9, a C12-C-13 ethoxylated primary alcohol having about 9 moles of ethylene oxide, and Neodol 91-10, a Cg-C-n ethoxylated primary alcohol having about 10 moles of ethylene oxide. Alcohol ethoxylates of this type have also been marketed by Shell Chemical Company under the trademark of Dobanol.

Dobanol 91-5 is an ethoxylated fatty alcohol of Cg-C ^ with an average of 5 moles of ethylene oxide, and Dobanol 25-7 is an ethoxylated fatty alcohol of C-J2-C-I5 with an average of 7 moles of ethylene oxide per mole of fatty alcohol. Other examples of suitable ethoxylated alcohols include Tergitol 15-S-7 and Tergitol 15-S-9, which are linear secondary alcohol ethoxylates that have been marketed by Union Carbide Corporation. The first is a mixed secondary alkaline ethoxylation product of C- | i to C15 with 7 moles of ethylene oxide, and the last one is a similar product, but with 9 moles of ethylene oxide being reacted. Other types of alcohol ethoxylates useful in the present compositions are non-ionic compounds of higher molecular weight, such as Neodol 45-11, which are similar condensation products of ethylene oxide of higher fatty alcohols, the fatty alcohol being higher than 14. at 15 carbon atoms, and the number of ethylene oxide groups per mole of about 11. Said products have also been marketed by Shell Chemical Company. If nonalonic alcohol alkoxylate surfactant is used as part of the non-aqueous liquid phase in the detergent compositions herein, it will preferably be present up to the level of about 1% to 60% of the structured liquid phase of the composition. More preferably, the alkoxylate alcohol component will comprise about 5% to 40% of the structured liquid phase. Most preferably, an akoxylate alcohol component will comprise from about 5% to 35% of the structured liquid phase of the detergent composition. The use of an alkoxylate alcohol in these concentrations in the liquid phase corresponds to a concentration of alkoxylate alcohol in the total composition of about 1% to 60% by weight, more preferably about 2% to 40% by weight, and very preferably from about 5% to 25% by weight, of the composition.

Another type of liquid non-aqueous surfactant which can be used in this invention are the block polymers of ethylene oxide (EO) -propylene oxide (PO). Materials of this type are well-known nonionic surfactants which have been marketed under the trademark Pluronic. These materials are formed by adding blocks of ethylene oxide portions to the ends of polypropylene glycol chains to adjust the surfactant properties of the resulting block polymers. Nonionic surfactants of EO-PO block polymers of this type are described in greater detail in Davidsohn and Milwidsky, Synthetic Detergents, 7a. ed., Longman Scientific and Technical (1987) p. 34-36 and pages. 189-191, and in the patents of E.U.A. 2,674,619 and 2,677,700. These publications are incorporated herein by reference. It is also thought that these non-ionic surfactants of the Pluronic type function as effective suspending agents for the particulate material which is dispersed in the liquid phase of the detergent compositions herein. Another possible type of non-aqueous liquid surfactant useful in the compositions herein, comprises polyhydroxy fatty acid amide surfactants. If present, the polyhydroxy fatty acid amide surfactants are preferably present at a concentration of from about 0.1 to about 8%. Materials of this type of nonionic surfactant are those having the formula: O CpH p + 1 R- C il- N i -Z wherein R is an alkyl or alkenyl of C9-? 7, p is from 1 to 6, and Z is glycityl derived from a reduced sugar or alkoxylated derivative thereof. Such materials include the N-methylglucamides of C12-C-18. Examples are N-methyl N-1-deoxyglucityl cocoamide and N-methyl N-1-deoxyglucityl oleamide. Methods for obtaining polyhydroxy fatty acid amides are known and can be found, for example, in Wilson, U.S. Pat. 2,965,576, and Schwartz, patent of E.U.A. No. 2,703,798, the disclosures of which are incorporated herein by reference. These materials and their preparation are described in greater detail in Honsa, patent of E.U.A. 5,174,937, issued December 26, 1992, which is also incorporated herein by reference. The amount of total liquid surfactant in the preferred non-aqueous structured liquid phase herein will be determined by the type and amounts of other components of the composition, and by the desired properties of the composition. Generally, the liquid surfactant may comprise from about 35% to 70% of the non-aqueous liquid phase of the compositions herein. More preferably, the liquid surfactant will comprise from about 50% to 65% of a structured non-aqueous liquid phase. This corresponds to a non-aqueous liquid surfactant concentration in the total composition, from about 15% to 70% by weight, more preferably from about 20% to 50% by weight, of the composition. iii. Non-aqueous nonaqueous organic solvents The liquid phase of the detergent compositions herein may also comprise one or more nonaqueous non-aqueous organic solvents. Said non-aqueous non-surfactant liquids are preferably those of low polarity. For purposes of this invention, "low polarity" liquids are those that have little, if any, tendency to dissolve one of the preferred types of particulate material used in the compositions herein, ie, the agents of peroxygen bleach, sodium perborate or sodium percarbonate. In this way, relatively polar solvents such as ethanol should not be used. Suitable types of low polarity solvents useful in the non-aqueous liquid detergent compositions herein include non-vicinal C 4 -C 8 alkylene glycols, lower alkylene glycol ethers of alkylene glycol, lower molecular weight polyethylene glycols, lower molecular weight methyl esters and amides, and similar. A preferred type of non-aqueous low polarity solvent for use in the compositions herein comprises the non-vicinal C4-C8 branched or straight chain alkylene glycols. Materials of this type include hexylene glycol (4-methyl-2,4-pentanediol), 1,6-hexanediol, 1,3-butylene glycol and 1,4-butylene glycol. The most preferred is hexylene glycol.

Another preferred type of low polarity non-aqueous solvent for use herein comprises the C2-C6 monoalkyl ethers of C2-C3 mono-, di-, tri- or tetraalkyleneglycol. Specific examples of such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monobutyl ether. The diethylene glycol monobutyl ether, the dipropylene glycol monobutyl ether and the butoxy propoxy propanol (BPP) are especially preferred. Compounds of this type have been sold commercially under the trademarks of Dowanol, Carbitol and Cellosolve. Another preferred type of non-aqueous low polarity organic solvent useful herein comprises lower molecular weight polyethylene glycols (PEGs). Such materials are those that have molecular weights of at least 150. PEGs of molecular weight from 200 to 600 are most preferred. Another preferred type of non-polar non-aqueous solvent comprises methyl ethers of lower molecular weight. Said materials are those of the general formula: R 1 -C (0) -OCH 3 J wherein R ranges from 1 to 18. Examples of suitable lower molecular weight methyl esters include methylacetate, methylpropionate, methyloctanoate and methyldodecanoate. The non-surfactant organic solvents, generally of low polarity and non-aqueous used, must of course be compatible and non-reactive with other components of the composition, for example, bleach and / or bleach activators used in the liquid detergent compositions herein. Said solvent component will generally be used in an amount of 1% to 70% by weight of the liquid phase. More preferably, the non-aqueous low polarity organic solvent will comprise from 10% to 60% by weight of the liquid phase, more preferably from 20% to 50% by weight of the structured liquid phase of the composition. The use of the non-surfactant solvent at these concentrations in the liquid phase corresponds to a concentration of non-surfactant solvent in the total composition of 1% to 50% by weight, more preferably 5% to 40% by weight, and most preferably 10% by weight. % to 30% by weight of the composition. iv. Mixtures of surfactant and non-surfactant solvents In systems that use non-aqueous surfactant liquids and nonaqueous non-surfactant solvents, the ratio of surfactant liquids: non-surfactants, for example, the ratio of alkoxylate alcohol: low polarity solvent, to a liquid phase structured containing surfactant can be used to vary the rheological properties of the finally formed detergent compositions. In general, the weight ratio of surfactant liquid: non-surfactant organic solvent will vary from about 50: 1 to 1: 50. More preferably, this ratio will vary from about 3: 1 to 1: 3, most preferably from about 2: 1 to 1: 2. v. Structuring Surfactant The non-aqueous liquid phase of the detergent compositions of this invention is prepared by combining the non-aqueous organic liquid diluents described above, with a surfactant which is selected generally, but not necessarily, to give structure to the liquid phase not aqueous of the detergent compositions herein. The structuring surfactants can be of the anionic, nonionic, cationic and / or amphoteric types. Preferred structuring surfactants are anionic surfactants such as alkyl sulphates, alkyl polyalkoxylate sulfates and linear alkylbenzene sulphonates. Another common type of anionic surfactant material that can optionally be added to the detergent compositions herein as a structurant, comprises carboxylate-type anionic surfactants. Carboxylate-type anionic surfactants include the C 1 -C 1 alkylalkoxycarboxylates (especially the EO ethoxycarboxylates 1 to 5) and the C 10 -C 18 sarcosinates, especially oleoylsarcosinates. Another common type of anionic surfactant material that can be used as a structurant comprises other sulfonated anionic surfactants such as the C8-C-8 parafinsulfonates and the C8-C18 olefinsulfonates. Structural anionic surfactants will generally comprise from about 1% to 30% by weight of the compositions herein.

As indicated, a preferred type of structuring anionic surfactant comprises primary or secondary alkyl sulfate anionic surfactants. Said surfactants are those produced by the sulphation of higher C8-C20 fatty albules. Conventional primary alkylsulfate surfactants have the general formula: ROS03"M + wherein R is typically a linear C8-C2o hydrocarbyl group, which may be straight or branched chain, and M is a water solubilizing cation. preferably, R is a C 10-14 alkyl, and M is an alkali metal, More preferably, R is about C 12, and M is sodium Conventional secondary alkyl sulfates can also be used as a structuring anionic surfactant for the liquid phase of the compositions herein The conventional secondary alkyl sulfate surfactants are those materials having the sulfate portion distributed randomly along the hydrocarbyl "base structure" of the molecule, which materials can be represented by the structure: CH 3 (CH2) n (CHOS? 3"M +) (CH2) mCH3 where m and n are integers of 2 or more, and the sum of m + n is typically around 9 to 1 5, and M is a cation of water solubilization. If used, the alkyl sulfates will generally comprise from about 1% to 30% by weight of the composition, more preferably from about 5% to 25% by weight of the composition. Non-aqueous liquid detergent compositions containing alkyl sulphates, peroxygen bleach agents and bleach activators are described in greater detail in Kong-Chan et al., WO 96/10073, cited on April 4, 1996, the application of which is incorporated in the present as a reference. Another preferred type of anionic surfactant material that can be optionally added to the non-aqueous laundry compositions herein as a structurant, comprises the alkyl polyalkoxylate sulphates. The alkyl polyalkoxylate sulphates are also known as alkylsulfates or alkoxylated alkyl ether sulphates. Said materials are those corresponding to the formula: R2-0- (CmH2mO) n-S03M wherein R2 is a C10-C22 alkyl group, m is from 2 to 4, n is from about 1 to 15, and M is a cation of salt formation. Preferably, R2 is a Ci2-C18 alkyl, m is 2, n is from about 1 to 10, and M is sodium, potassium, ammonium, alkylammonium or alkanolammonium. More preferably, R2 is a C12-C16 alkyl, m is 2, n is from about 1 to 6, and M is sodium. Counterions of ammonium, aikammonium and alkanolammonium are preferably avoided when used in the compositions herein because of their incompatibility with peroxygen bleaching agents. If used, the alkyl polyalkoxylate sulphates can also generally comprise from about 1% to 30% by weight of the composition, more preferably from about 5% to 25% by weight of the composition.

Non-aqueous liquid detergent compositions containing alkyl polyalkoxylate sulfates, in combination with polyhydroxy fatty acid amides, are described in greater detail in Boutique et al, PCT Application No. US96 / 04223, the application of which is incorporated herein by reference. The most preferred type of anionic surfactant for use as a structurant in the compositions herein, comprises the linear alkylbenzene sulphonate (LAS) surfactants. In particular, said LAS surfactants can be formulated in a specific type of powder containing the anionic surfactant which is especially useful for incorporation into the non-aqueous liquid detergent compositions of the present invention. Said powder comprises two distinct phases. One of these phases is insoluble in the non-aqueous organic liquid diluents used in the compositions herein; the other phase is soluble in non-aqueous organic liquids. It is the insoluble phase of this powder containing preferred anionic surfactant, which can be dispersed in the non-aqueous liquid phase of the preferred compositions herein, and which forms a network of small aggregate particles that allow the final product to suspend stably other particulate solid materials in the composition. Said preferred anionic surfactant-containing powder is formed by co-drying an aqueous suspension containing essentially (a) one or more alkali metal salts of C10-16 linear alkylbenzenesulfonic acids. and (b) one or more non-surfactant diluent salts. Said suspension is dried to a solid material, generally in powder form, which comprises the soluble and insoluble phases. The linear alkylbenzene sulphonate (LAS) materials that are used to form the powder containing the preferred anionic surfactant are well known materials. Said surfactants and their preparation are described, for example, in the patents of E.U.A. 2,220,099 and 2,477,383, incorporated herein by reference. Linear straight-chain potassium and sodium alkylbenzenesulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 14 are especially preferred. Cn- LAS, eg, C-12, are especially preferred. , of sodium. Anionic alkylbenzenesulfonate surfactants are generally used in the slurry that forms powder in an amount of about 20 to 70% by weight of the suspension, more preferably from about 20% to 60% by weight of the suspension. The powder-forming suspension also contains a non-surfactant organic or inorganic salt component which is co-dried with LAS to form the powder containing the two-phase anionic surfactant. Said salts can be any of the known halides, sulfates, citrates, carbonates, sulfates, borates, succinates, sulfosuccinates and the like of sodium, potassium or magnesium. Sodium sulfate, which is usually a byproduct of LAS production, is the preferred non-surfactant diluent salt for use herein. Salts that function as hydrotropes, such as sodium sulfosuccinate, can also be usefully included. The non-surfactant salts are generally used in the aqueous suspension, together with the LAS, in amounts ranging from about 1 to 50% by weight of the suspension, more preferably from about 5% to 40% by weight of the suspension. Salts that function as hydrotropes can preferably comprise up to about 3% by weight of the suspension. The aqueous suspension containing the diluent salt and LAS components described above, can be dried to form the powder containing the anionic surfactant preferably added to the non-aqueous diluents, to prepare a structured liquid phase within the compositions of the invention. I presented. Any conventional drying technique can be used, for example, spray drying, drum drying, etc., or a combination of drying techniques. The drying should be carried out until the residual water content of the solid material being formed is within the range of about 0.5% to 4% by weight, more preferably about 1% to 3% by weight. The powder containing the anionic surfactant produced by the drying operation constitutes two distinct phases, one of which is soluble in the inorganic liquid diluents that are used herein, and one of which is insoluble in the diluents. The insoluble phase in the powder containing the anionic surfactant generally comprises from about 10% to 45% by weight of the powder, more preferably from about 15% to 35% by weight of the powder. The powder containing the anionic surfactant and resulting after drying, may comprise from about 45% to 94%, more preferably from about 60% to 94%, by weight of the alkylbenzenesulfonic acid salt powder. Such concentrations are generally sufficient to provide from about 0.5% to 60%, more preferably from about 15% to 60%, by weight of the total detergent composition that is finally prepared, of the alkybenzenesulfonic acid salts. The powder containing the anionic surfactant can comprise from about 0.45% to 45% by weight of the total composition that is finally prepared. After drying, the powder containing the anionic surfactant will also generally comprise from about 2% to 50%, more preferably from about 2% to 25% by weight of the powder of the non-surfactant salts. After it is dried to the desired degree, the combined LAS / salt material can be converted to the flake or powder form by any known milling or grinding method. Typically, by the time such material is combined with the non-aqueous organic solvents to form the structured liquid phase of the compositions herein, the particle size of this powder will vary from 0.1 to 2000 microns, more preferably from about 0.1 to 100 microns. 1000 micras A structured liquid phase containing the surfactant of preferred detergent compositions herein can be prepared by combining the non-aqueous organic diluents described above with the powder containing the anionic surfactant as described above. Said combination results in the formation of a structured liquid phase containing surfactant. The conditions for obtaining this preferred structured liquid phase component combination are described in more detail later in the "preparation and use of the composition" section. As described above, the formation of a structured liquid phase containing surfactant allows the stable suspension of colored specks and other solid materials into functional particles within the preferred detergent compositions of this invention. Other surfactants suitable for use in the present invention include nonionic surfactants, specifically, polyhydroxy fatty acid amides of the formula: O R 1 R-C il- N i -Z wherein R is C9-? 7 alkyl or alkenyl, Ri is a methyl group, and Z is glycityl derived from a reducing sugar or alkoxylated derivative thereof. Examples are N-methyl N-1-deoxyglucityl cocoamide and N-methyl N-1-deoxyglucityl oleamide. Methods for obtaining polyhydroxy fatty acid amides are known and can be found in Wilson, U.S. Pat. 2,965,576, and Schwartz, patent of E.U.A. 2,703,798, the descriptions of which are incorporated herein by reference. Preferred surfactants for use in the detergent compositions described herein, are amine-based surfactants of the general formula: wherein Ri is an alkyl group of C6-C? 2; n is from about 2 to about 4, X is a linking group that is selected from NH, CONH or COO, and O or X may be absent; and R3 and R4 are individually selected from H, C C alkyl or (CH2-CH2-0 (R5)), wherein R5 is H or methyl. Especially preferred amine-based surfactants include the following: R? - (CH2) 2-NH2 R? -C (O) -NH- (CH2) 3-N (CH3) 2 wherein R1 is a C6-C2 alkyl group, and R5 is H or CH3. Particularly preferred amines for use in the surfactants defined above include those selected from the group consisting of octyl amine, hexyl amine, decyl amine, dodecyl amine, bis (hydroxyethyl) amine of C8-C-12, bis (hydroxyisopropyl) ) C8-C2 amine, C8-C2-amidopropyldimethylamine, or mixtures thereof. In a highly preferred embodiment, the amine based surfactant is described by the formula: R1-C (0) -NH- (CH2) 3-N (CH3) 2 wherein Ri is C8-C2alkyl. saw. Particulate solid materials The non-aqueous detergent compositions herein preferably comprise from about 0.01% to 50% by weight, more preferably from about 0.2% to 30% by weight, of solid particulate material which is dispersed and suspended within the liquid phase. Generally, said particulate material will vary in size from about 0.1 to 1500 microns, more preferably from about 0.1 to 900 microns. Most preferably, said material will vary in size from about 5 to 200 microns. The particulate material used herein may comprise one or more types of detergent composition components which, in particulate form, are substantially insoluble in the nonaqueous liquid phase of the composition. The types of particulate materials that can be used are described in detail below: Water-Based Heavy-Duty Liguid Detergents Surfactants The present invention also comprises aqueous-based liquid detergent compositions. Water-based liquid detergent compositions preferably comprise from about 10% to about 98%, preferably from about 30% to about 95% by weight, of an aqueous liquid vehicle that is preferably water. Additionally, the aqueous liquid detergent compositions of the present invention comprise a surfactant system which preferably contains one or more detersive surfactant coagents in addition to the branched surfactants described above. Additional surfactant coagents may be selected from nonionic detersive surfactant, anionic detersive surfactant, zwitterionic detersive surfactant, amine oxide detersive surfactant, and mixtures thereof. The surfactant system typically comprises from about 5% to about 70%, preferably from about 15% to about 30% by weight, of the detergent composition. i. Anionic Surfactant Anionic Surfactants include Cj? -C-) 8 (LAS) aralkylbenzenesulfonates and C10-C20 (AS) random and branched chain primary alkylsulphates, the secondary alkyl sulfates (2.3) of C-io- C-is of the formula CH3 (CH2) x (CHOS? 3-M +) CH3 and CH3 (H2) and (CHOS? 3-M +) CH2CH3, wherein xy (y + 1) are integers of at least about 7, preferably at least about 9, and M is a cation of solubilization in water, especially sodium, unsaturated sulfates such as oleyl sulfate, the alkylalkoxy sulfates of C- \ QC ^ \ Q ("AEXS", especially 1-7 ethoxy sulfates EO), alkylalkoxycarboxylates of Clo_Cl 8 (especially the 1-5 ethoxycarboxylates EO), the glycerol ethers of C-? Or-18- the alkyl polyglucosides of CI QC S and their sulphated polyglucosides corresponding, and alphasulfonated fatty acid esters of C ^ 2-C18. Generally speaking, the anionic surfactants useful herein are described in U.S. Pat. No. 4,285,841 by Barrat et al, issued August 25, 1981, and in the U.S. patent. No. 3,919,678 by Laughiin et al, issued December 30, 1975. Useful anionic surfactants include water-soluble salts, particularly the alkali metal, ammonium and alkylolammonium salts (eg, monoethanolammonium or triethanolammonium) of reaction products of organic sulfuric acid having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and an ester group of sulfonic acid or sulfuric acid. (Included in the term "alkyl" is the alkyl portion of aryl groups). Examples of this group of synthetic surfactants are the alkyl sulfates, especially those obtained by sulfating the higher alcohols (CQ-C-Q carbon atoms), such as those produced by reducing the tallow glycerides or coconut oil. Other anionic surfactants herein, are the water soluble salts of ethylene oxide ether sulfates of alkylphenol containing from about 1 to about 4 ethylene oxide units per molecule, and from about 8 to about 12 carbon atoms. in the alkyl group. Other anionic surfactants useful herein include the water soluble salts of alpha-sulfonated fatty acid esters containing from about 6 to about 20 carbon atoms in the fatty acid group, and from about 1 to about 10 atoms. of carbon in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to about 9 carbon atoms in the acyl group, and from about 9 to about 23 carbon atoms in the alkane portion; water-soluble salts of olefin sulphonates containing from about 12 to about 24 carbon atoms; and β-alkyloxy-alcansulfonates containing from about 1 to about 3 carbon atoms in the alkyl group, and from about 8 to about 20 carbon atoms in the alkane portion. Particularly preferred anionic surfactants herein are the alkylpolyethoxylate sulfates of the formula: RO (C2H40) xS? 3-M + wherein R is an alkyl chain having from about 10 to about 22 carbon atoms, saturated or unsaturated , M is a cation which makes the compound water soluble, especially an alkali metal ammonium or substituted ammonium cation, and x averages from about 1 to about 15. Preferred alkyl sulfate surfactants are the primary and secondary alkyl sulfates Non-ethoxylated C-12-15- Under washing conditions in cold water, ie, less than about 18.3 ° C, it is preferred that there is a mixture of said ethoxylated and non-ethoxylated alkyl sulphates. Examples of fatty acids include capric, lauric, myristic, palmitic, stearic, arachidic and behenic acids. Other fatty acids include palmitoleic, oleic, linoleic, linolenic and ricinoleic acids. ii. Nonionic Surfactant Conventional non-ionic and amphoteric surfactants include alkyl ethoxylates of C-J2-C8 (AE), including so-called narrow peak alkyl ethoxylates, and alkylphenol alkoxylates of C < \ Q-C- | 2 (especially ethoxylates and ethoxy / mixed propoxy). The N-alkylamides of polyhydroxy fatty acid of C-J Q-CI S- Typical examples include the N-methyl glucamides of C ^ -C-J S- See WO 9,206,154. Other surfactants derived from sugar include the polyhydroxy fatty acid N-alkoxyamides, such as N- (3-methoxypropyl) glucamide of C- | 2_C 8- For low foaming, the N-propyl to N-hexyl can be used Ci2-Ci8 glucamides- Conventional C- | o-C2? soaps can also be used? - If high foaming is desired, the branched-chain soaps of C-jo-Ci6-Examples of nonionic surfactants can be used. are described in the US nt No. 4,285,841 by Barrat et al, issued August 25, 1981. Preferred examples of these surfactants include ethoxylated alcohols and ethoxylated alkylphenols of the formula R (OC2H4) nOH, wherein R is selected from the group consisting of hydrocarbon radicals. aliphatic containing from about 8 to about 15 carbon atoms, and alkylphenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15. These surfactants are described in more detail in the US nt No. 4,284,532 by Leikhim et al, issued August 18, 1981. Particularly preferred are the ethoxylated alcohols having an average of about 10 to about 15 carbon atoms in the alcohol, and an average degree of ethoxylation of about 6. to about 12 moles of ethylene oxide per mole of alcohol. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are included in normal texts, including betaines and sulfobetaines (sultaines) of C- | 2-C-j8- iii. Amine Oxide Surfactants The compositions herein also contain amine oxide surfactants of the formula: R1 (EO) x (PO) and (BO) zN (0) (CH2R ') 2-qH2? (I) In general, it can be seen that structure (I) provides a long chain portion R (EO) x (PO) and (BO) z and two short chain portions, CH2 '. R 'is preferably selected from hydrogen, methyl and -CH2OH. In In general, R is a primary or branched hydrocarbyl portion that can be saturated or unsaturated and, preferably, R is a primary alkyl moiety. 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 may be a little longer, having a Chain length on the scale of C-J2-C24- The general formula also covers oxides of amine, where x + y + z = 0, R = C8-Ci8. R 'is H and q is from 0 to 2, preferably 2. These amine oxides are polished by the alkyldimethylamine oxide of C ^ 2_14. hexadecyldimethylamine oxide, octadecylamine oxide and its hydrates, especially the dihydrates, as described in the U.S. nts. 5,075,501 and 5,071, 594, incorporated herein by reference. The invention also encompasses amine oxides, wherein x + y + z is different from O, specifically x + y + z is from about 1 to about 10, R1 is a primary alkyl group containing from about 8 to about 24 carbons, preferably from about 12 to about 16 carbon atoms; in these embodiments, y + z is preferably 0, and x is preferably from about 1 to about 6, more preferably from about 2 to about 4; EO represents ethyleneoxy; PO represents propyleneoxy; and BO represents butyleneoxy. Said amine oxides can be prepared by conventional synthesis methods, for example, by the reaction of alkyl ethoxy sulfates with dimethylamine, followed by oxidation of the ethoxylated amine with hydrogen peroxide. The highly preferred amine oxides of the present are solids at room temperature, and more preferably have melting points in the range of 30 ° C to 90 ° C. Amine oxides suitable for use herein are commercially manufactured by various suppliers, including Akzo Chemie, Ethyl Corp. and Procter &; Gamble. See the McCutcheon compilation and the Kirk-Othmer review article for alternative amine oxide manufacturers. The commercially available preferred amine oxides are ADMOX 16 and ADMOX 18 dihydrated solids, ADMOX 12 and especially ADMOX 14 from Ethyl Corp. Preferred embodiments include dodecyldimethylamine dihydrate oxide, hexadecyldimethylamine oxide dihydrate, octadecyldimethylamine oxide dihydrate, hexadecyltris oxide. (ethylenoxy) d, methylamine, tetradecyldimethylamine oxide dihydrate, and mixtures thereof. While in some of the preferred embodiments R 'is H, there is some amplitude with respect to the fact that R' is slightly longer than H. Specifically, the invention further encompasses embodiments wherein R 'is CH2OH, such as hexadecylbis oxide (2). -hydroxyethyl) amine, tallowbis (2-hydroxyethyl) amine oxide, stearylbis (2-hydroxyethyl) amine oxide and oleylbis (2-hydroxyethyl) amine oxide.

Heavy-Duty Gel Laundry Detergent Compositions The present invention encompasses heavy-duty laundry gel detergent compositions comprising, by weight of the composition: a) from about 15% to about 40% of an anionic surfactant component the which comprises, by weight of the composition: (i) from about 5% to about 25% alkylpolyethoxylate sulphates, wherein the alkyl group contains from about 10 to about 22 carbon atoms, and the polyethoxylate chain contains about 0.5 to about 15, preferably from 0.5 to about 5, more preferably from 0.5 to about 4, portions of ethylene oxide; and (ii) from about 5% to about 20% fatty acids; and b) one or more of the following ingredients: detersive amine, modified polyamine, polyamide-polyamine, polyethoxylated polyamine polymers, quaternary ammonium surfactants, suitable acid or electrolyte equivalents thereof, and mixtures thereof. The compositions herein may also contain one or more additional detersive additives selected from the group consisting of non-citrate builders, optical brighteners, soil release polymers, dye transfer inhibitors, polymeric dispersing agents, enzymes, suppressants. of foam, colorants, perfumes, filler salts, hydrotropes, anti-redeposition agents, anti-bleaching agent, dye fixing agents, pellet / fluff reducing agents, and mixtures thereof. The compositions herein have a viscosity at a shear rate of 20 sec "1, from about 100 cp to about 4,000 cp, preferably from about 300 cp to about 3,000 cp, more preferably about 500 cp a approximately 2,000 cp, and are stable during storage.The compositions herein are structured and have a specific rheology.Rheology can be represented by the following formula:? =? oW1) where? is the viscosity of the liquid at a speed of shear stress,? 0 is the viscosity at infinite shear velocity,? is the shear rate, n is the shear rate, and K is the consistency index.As used herein, the term "structured" indicates a heavy-duty liquid composition having a liquid crystalline lamellar phase and an infinite shear viscosity (? 0) value. re 0 and about 3,000 cp (centipoise), a value of shear index (n) less than about 0.6, a value of consistency index, K, greater than about 1, 000, and a viscosity (?) measured at 20 sec "1, less than about 10,000 cp, preferably less than about 5,000 cp. Under conditions of low stress levels, a viscosity of "zero shear stress" is greater than about 100,000 cp, where "zero shear stress" means a shear rate of 0.001 sec "1 or less. The compositions herein, which is obtained by plotting the viscosity against tension, is greater than 0.2 Pa. These rheological parameters can be measured using any commercially available rheometer, such as the Carrimed CSL model 100. The compositions herein are clear or translucent , that is, they do not opaque.

Electrolytes Without being limited by theory, it is thought that the presence of electrolytes serves to control the viscosity of the gel compositions. In this way, the gel nature of the compositions herein is affected by the choice of surfactants, and by the amount of electrolytes present. In preferred embodiments herein, the compositions will further comprise from 0% to about 10%, more preferably from about 2% to about 6%, even more preferably from about 3% to about 5%, of a suitable electrolyte or acid equivalent thereof. Sodium citrate is a highly preferred electrolyte for use herein. The compositions herein may optionally contain from about 0% to about 10%, by weight, of solvents and hydrotropes. Without being limited by theory, it is thought that the presence of solvents and hydrotropes may affect the structured nature against sotropic compositions; "solvent" means the solvents commonly used in the detergent industry, including alkyl monoalcohol, dialcohols and trialcohols, ethylene glycol, propylene glycol, propanediol, ethanediol, glycerin, etc. By "hydrotrope" we mean the hydrotropes that are commonly used in the detergent industry, including short chain surfactants that help solubilize other surfactants. Other examples of hydrotropes include eumeno, xylene, toluenesulfonate, urea, C8 or shorter chain alkylcarboxylates, and Cs or shorter chain ethoxylated alkyl sulfates and sulfates.

Modified Polyamine The compositions herein may comprise at least about 0.05%, preferably from about 0.05% to about 3%, by weight, of a modified, dispersible or water soluble polyamine agent, said agent comprising a structure of polyamine base corresponding to the formula: wherein each R1 is independently arylene, alkenylene or C2-C5 alkylene each R2 is independently H or a portion of the formula OH [(CH2)? O] n, wherein x is from about 1 to about 8, and n is from about 10 to about 50; W is 0 or 1; x + y + z is from about 5 to about 30; and B represents a continuation of this structure by branching; and wherein said polyamine before alkylation has an average molecular weight of from about 300 to about 1200. In preferred embodiments, R 1 is C 2 -C 4 alkylene, more preferably ethylene; R2 is OH [CH2CH20] n, wherein n is from about 15 to about 30, more preferably n is from about 20. The average molecular weight of the polyamine before alkylation is from about 300 to about 1200, more preferably from about 500 to about 900, still more preferably from about 600 to about 700, even more preferably from about 600 to about 650. In another preferred embodiment, R1 is C2-C alkylene, more preferably ethylene; R2 is OH [CH2CH0] n, wherein n is from about 10 to about 20, more preferably n is from about 15. The average molecular weight of the polyamine before alkylation is from about 100 to about 300, more preferably from about 150 to about 250, even more preferably from about 180 to about 200.

Polyamide Polyamines The polyamide polyamines useful herein will generally comprise from about 0.1% to 8% by weight of the compositions herein. More preferably, said polyamide-polyamine materials will comprise from about 0.5% to 4% by weight of the composition. Most preferably, these polyamide polyamines will comprise from about 1% to 3% by weight of the composition. The polyamide-polyamine materials used in this invention are those having repeating substituted amido-amine units corresponding to the following general structural formula No. I: Structural Formula No. I In structural formula No. I, R1; R2 and R5 are each independently alkylene of C ^, alkarylene of C? -4 or arylene. It is also possible to completely eliminate R-i, so that the polyamide-polyamine is derived from oxalic acid. Also in structural formula No. I, R3 is H, epichlorohydrin, an azetidinium group, an epoxypropyl group or a dimethylaminohydroxypropyl group, and R can be H, CrC alkyl, C4 alkaryl, or aryl. R 4 can also be any of the above groups condensed with C 1 -C 4 alkylene oxide. R1 is preferably butylene, and R2 and R5 are preferably ethylene. R3 is preferably epichlorohydrin. R4 is preferably H. The polyamide-polyamine materials useful herein can be prepared by reacting polyamines such as diethylenetriamine, triethylenetetraamine, tetraethylenepentamine or dipropylenetriamine with C2C2carboxylic acids such as oxalic, succinic, glutaric, adipic and diglicaiico. Said materials can then be further derived by reaction, for example, with epichlorohydrin. The preparation of said materials is described in greater detail in Keim, patent of E.U.A. 2,296,116, issued February 23, 1960; Keim, patent of E.U.A. 2,296,154, issued February 23, 1960, and Keim, patent of E.U.A. 3,332,901, issued July 25, 1967. Preferred polyamide-polyamine agents for use herein are marketed by Hercules, Inc., under the trademark Kymene®. Especially useful are Kymene 557H® and Kymene 557LX®, which are epichlorohydrin adducts of polyamide-polyamines, which are the reaction products of diethylenetriamine and adipic acid. Other suitable materials are those marketed by Hercules under the trademarks Reten® and Delsette®, and by Sandoz under the trademark Cartaretin®. These polyamide-polyamine materials are marketed in the form of aqueous suspensions of the polymeric material containing, for example, about 12.5% by weight solids.

Detersive amine Amine surfactant agents suitable for use herein include detersive amines in accordance with the formula: wherein Ri is an alkyl group of C6-C? 2; n is from about 2 to about 4, X is a linking group that is selected from NH, CONH, COO, or O u X may be absent; and R3 and R4 are individually selected from H, C1-C4 alkyl or (CH2-CH2-0 (R5)), wherein R5 is H or methyl.

Preferred amines include the following: R1- (CH2) 2-NH2 (1) R1-0- (CH2) 3-NH2 (2) R1-C (0) -NH- (CH2) 3-N (CH3) 2 (3) CH2CH (OH) R5 R- N (4) CH2CH (OH) R5 wherein Ri is a C6-C2 alkyl group, and R5 is H or CH3. In a highly preferred embodiment, the amine is described by the formula: R C (0) -NH- (CH 2) 3-N (CH 3) 2 wherein Ri is C 8 -C 2 alkyl. Particularly preferred amines include those selected from the group consisting of octylamine, hexylamine, decylamine, dodecylamine, Cs-C2 bis (hydroxyethyl) amine, C8-C2 bis (hydroxyisopropyl) amine and C8-C2 amidopropyl dimethylamine. , and mixtures thereof. If used, the detersive amines comprise from about 0.1% to about 10%, preferably from about 0.5% to about 5%, by weight of the composition.

Quaternary Ammonium Surfactants The cationic surfactants that can be used herein include quaternary ammonium surfactants of the formula: wherein R ^ and R2 are individually selected from the group consisting of CC alkyl, C4 hydroxyalkyl, benzyl and - (C2H 0) xH, wherein x has a value of from about 2 to about 5; X is an anion; and (1) R3 and R4 are in each case a C6-C-? 4 alkyl or R3 is a C-C-is alkyl and R4 is selected from the group consisting of C1-C10 alkyl, hydroxyalkyl of Cr C10 , benzyl and - (C2H40) xH, wherein x has a value of 2 to 5. Preferred quaternary ammonium surfactants are the chloride, bromide and methylisulfate salts. Examples of long-chain quaternary alkyl quaternary ammonium surfactants are those in which R i, R 2 and R 4 are each methyl and R 3 is a C 8 -C 6 alkyl; or wherein R3 is a C8-C18 alkyl, and R1, R2 and R4 are selected from the methyl and hydroxyalkyl portions. Also desirable lauryltrimethylammonium chloride, myristyltrimethylammonium chloride, palmitiltrimetilamonio chloride, cocotrimethylammonium chloride, cocotrimethylammonium metiisulfato of cocodimetilmonohidroxietilamonio chloride, metiisulfato of cocodimetilmonohidroxietilamonio of cocodimetilmonohidroxietilamonio chloride, metiisulfato of cocodimetilmonohidroxietilamonio chloride, dialkyl (C12-C1) dimethylammonium , and mixtures thereof. ADOGEN 412 ™, a lauryl dimethyl ammonium chloride commercially available from Witco, is also desirable. Other desirable surfactants are lauryltrimethylammonium chloride and myristyltrimethylammonium chloride. The alkoxylated quaternary ammonium surfactants (AQA) useful in the present invention are of the general formula: R 1 ApR4 X "R2 / (D wherein R1 is an alkyl or alkenyl portion containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, more preferably from about 10 to about 14 carbon atoms; R2 and R3 are each independently alkyl groups containing from about 1 to about 3 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 to provide electrical neutrality; A is selected from C1-C4 alkoxy, especially ethoxy (i.e., -CH2CH20-), propoxy or butoxy, and mixtures thereof. same, and for formula I, p is from about 2 to about 30, preferably 2 to about 15, more preferred 2 to about 8, and for formula II, p is from about 1 to about 30, preferably from 1 to about 4, and q is from about 1 to about 30, preferably from 1 to about 4, and most preferably p and q are 1. Other quaternary surfactants include ammonium surfactants such as alkyldimethylammonium halides, and the surfactants having the formula: [R2 (OR3) and] [R4 (OR3) and] 2R5N +? - in that R2 is an alkyl or alkylbenzyl group having from about 8 to about 18 carbon atoms in the alkyl chain , each R3 is selected from the group consisting of -CH2CH2-, -CH2CH (CH3) -, -CH2CH (CH2OH) -, CH2CH2CH2-, and mixtures thereof; each R4 is selected from the group consisting of C -? - C alkyl, C -? - C4 hydroxyalkyl, benzyl, ring structures which are formed by joining the two groups R4, -CH2CHOHCHOHCOR6CHOH-CH2OH, wherein R6 is any hexose or hexose polymer having a molecular weight less than about 1000 and hydrogen when and is not O; R5 is the same as R4 or is an alkyl chain in which the total number of carbon atoms of R2 plus R5 is not more than about 18; each y is from 0 to approximately 10 and the sum of the values of y is from 0 to approximately 15; and X is any compatible anion.

Polyethoxylated Polyamine Polymers Another use in the form of a polymer dispersant herein includes polyethoxylated polyamine (PPP) polymers. Preferred polyethoxylated polyamines useful herein are generally polyalkyleneamines (PAA), polyalkyleneamines (PAI), preferably polyethyleneamines (PEA), polyethyleneimines (PEI). A common polyalkyleneamine (PAA) is tetrabutylenepentamine. PEAs are obtained by reactions involving ammonia and ethylene dichloride, followed by fractional distillation. The common AEPs obtained are triethylene tetramine (TETA) and tetraethylenepentamine (TEPA). Above the pentamines, ie the hexamines, heptamines, octamines and possibly nonamines, the congenically derived mixture does not appear to be separated by distillation and may include other materials, such as cyclic amines and particularly piperazines. Cyclic amines with side chains in which nitrogen atoms appear may also be present. See the patent of E.U.A. 2,792,372, Dickinson, issued May 14, 1957, which describes the preparation of PEA. Polyethoxylated polyamines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst, such as carbon dioxide, sodium disulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for preparing these polyamine base structures are set forth in the U.S. patent. 2,182,306, Ulrich et al., Issued December 5, 1939; the patent of E.U.A. 3,033,746, Mayle et al., Issued May 8, 1962; the patent of E.U.A. 2,208,095, Esselmann et al., Issued July 16, 1940; the patent of E.U.A. 2,806,839, Crowther, issued September 17, 1957; and the patent of E.U.A. 2,553,696, Wilson, issued May 21, 1951. Optionally, for the polyethoxylated polyamine preferred polymers useful for this invention are alkoxylated quaternary diamines of the general formula: wherein R is selected from linear or branched C2-C-? 2 alkylene, C3-C12 hydroxyalkylene, C4-C12 hydroxyalkylene, C8-C2 dialkylarylene, [(CH2CH20) qCH2CH2] - and -CH2CH (OH CH20- (CH2CH20) qCH2CH (OH) CH2] -, wherein q is from about 1 to about 100. Each Ri is independently selected from C- | -C4 alkyl, C7-C-? 2 alkylaryl or A. A is of the formula wherein R3 is selected from H or Ct-C3 alkyl, n is from about 5 to about 100 and B is selected from H, CrC4 alkyl, acetyl or benzoyl; X is a water soluble anion. In preferred embodiments, R is selected from C to C8 alkylene, Ri is selected from C2 alkyl and C2-C3 hydroxyalkyl, and A is: wherein R3 is selected from H or methyl, and n is from about 10 to about 50. In another preferred embodiment, R is linear or branched Ce, Ri is methyl, R3 is H and n is from about 20 to about 50. Additional dispersants of alkoxylated quaternary polyamine that can be used in the present invention are of the general formula : wherein R is selected from straight or branched C2-C2 alkylene, C3-C2 hydroxyalkylene, C4-C2 hydroxyalkylene, C8-C2-dialkylarylene, [(CH2CH20) qCH2CH2] - and - CH2CH (OH) CH20- (CH2CH20) qCH2CH (OH) CH2] -, in which q is from about 1 to about 100. If present, each Ri is independently selected from C -? - C alkyl, C7 alkylaryl C-t2 or A. Ri may be absent on certain nitrogens; however, at least three nitrogens must be quaternized. A is of the formula: wherein R3 is selected from H or C1-C3 alkyl, n is from about to about 100, and B is selected from H, C? -C alkyl, acetyl or benzoyl; m is from about 0 to about 4, and X is a water soluble anion. In preferred embodiments, R is selected from alkylene C4 to C8, R1 is selected from C1-C2 alkyl or C2-C3 hydroxyalkyl, and A wherein R3 is selected from H or methyl, and n is from about 10 to about 50; and m is 1. In another preferred embodiment, R is linear or branched Ce, R1 is methyl, R3 is H and n is from about 20 to about 50, and m is 1. The levels of these polyethoxylated polyamine polymers that are used can vary from about 0.1% to about 10%, typically from about 0.4% to about 5%, by weight. These polyethoxylated polyamine polymers can be synthesized, following the methods described in the U.S.A. No. 4,664,848, or other methods known to those skilled in the art.

Anionic Surfactant The anionic surfactant component contains alkylethoxylate sulfates and may contain other anionic surfactants other than soap or mixtures thereof. Generally speaking, useful anionic surfactants are disclosed herein, in the U.S. patent. No. 4,285,841, Barrat et al, issued August 25, 1981 and in the U.S. patent. No. 3,919,678, Laughiin et al, issued December 30, 1975, both incorporated herein by reference. Useful anionic surfactants include water-soluble salts, particularly the alkali metal, ammonium and alkylammonium salts (eg, monoethanolammonium or triethanolammonium), of organic sulfuric reaction products having in their molecular structure an alkyl group containing about 10. to about 20 carbon atoms or a sulfonic acid group or sulfuric acid ester. (Included in the term "alkyl" is in the alkyl portion of the aryl groups). Alkylsuiphates, especially those obtained by sulfurizing higher alcohols (8-18 carbon atoms), such as those produced by reducing tallow glycerides or coconut oil, are examples of this group of synthetic surfactants. Particularly valuable are linear straight-chain alkylbenzene sulphonates in which the average number of carbon atoms in the alkyl group is from about 1 to 13, abbreviated as C ??-C, 3LAS.

Other anionic surfactants herein are water soluble salts are alkylphenolethelene oxide ether sulfates containing from about 1 to about 4 ethylene oxide units per molecule and from about 8 to about 12 carbon atoms in the alkyl group. Other anionic surfactants useful herein include water-soluble salts of esters of α-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane portion; water-soluble salts of olefin sulphonates containing from about 12 to 24 carbon atoms; and β-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane portion. The alkyl polyethoxylate sulfates useful herein are of the formula RO (C2H40) xS03"M + in which R is an alkyl chain having from about 10 to about 22 carbon atoms, saturated or unsaturated, M is a cation which makes soluble in water the compound, especially an alkali metal, ammonium or substituted ammonium cation, and x is an average of about 0.5 to about 15. Preferred alkyl sulfate surfactants are the non-ethoxylated primary and secondary C12-15 alkyl sulphates. with cold water, that is, less than about (18.3 ° C), it is preferred that there be a mixture of three ethoxylated and non-ethoxylated alkyl sulfates.

Fatty acids In addition, the anionic surfactant component comprises fatty acids. These include saturated and / or unsaturated fatty acids obtained from natural sources or prepared synthetically. Examples of fatty acids include capric, lauric, myristic, palmitic, stearic, arachidic and behenic acids. Other fatty acids include palmitoleic, oleic, linoleic, linolenic, and ricinoleic acids.

Nonionic Detergent Surfactants Suitable non-ionic detergent surfactants are generally disclosed in US Pat. 3,929,678 Laughiin et al., Issued December 30, 1975, and the US patent. No. 4,285,841, Barrat et al, issued August 25, 1981. Exemplary non-limiting classes of useful nonionic surfactants include: alkyl ethoxylates ("AE") of Cs-C-is, with OE of about 1-22, including so-called narrow peak alkyl ethoxylates and C6-C12 alkylphenyl alkoxylates (especially mixed ethoxy-propoxy ethoxylates), alkyldialkylamine oxide, alkanoyl glucose amide and mixtures thereof. If nonionic surfactants are used, the compositions of the present invention will preferably contain up to about 10%, preferably from 0% to about 5%, more preferably from 0% to about 3%, by weight of a nonionic surfactant. Ethoxylated alcohols and ethoxylated alkylphenols of the formula R (OC2H) nOH are preferred, wherein R is selected from the group consisting of aliphatic hydrocarbon radicals containing between about 8 to 15 carbon atoms and alkylphenyl radicals in which the alkyl groups they contain from about 8 to about 12 carbon atoms and the average value of n is from about 5 to about 15. These surfactants are described in more detail in the US patent No. 4,284,532, Leikhim et al, issued August 18, 1981. Ethoxylated alcohols having an average of about 10 to about 15 carbon atoms in alcohol and an average degree of ethoxylation of about 6 to about 12 are particularly preferred. moles of ethylene oxide per mole of alcohol. Other nonionic surfactants for use herein include: The condensates of polyethylene oxide, polypropylene and polybutylene of alkylphenols. In general, they prefer polyethylene oxide condensates. These compounds include the condensation products of the alkylphenols having an alkyl group containing from about 6 to about 12 carbon atoms either in a straight chain or branched chain configuration with the ethylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to about 5 to about 25 moles of ethylene oxide per mole of alkylphenol. Commercially available nonionic surfactants of this type include Igepal® CO-630, distributed by the GAF Corporation; and Triton® X-45, X-114, X-100, and X-102, all distributed by the Rohm & Haas Company. These compounds are commonly referred to as alkylphenolaxylates (eg, alkylphenol ethoxylates). The condensation products of the aliphatic alcohols with about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol may be either straight or branched, primary or secondary and generally contains from about 8 to about 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 10 to about 20 carbon atoms with from about 2 to about 18 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants include Tergitol® 15-S-9 (the condensation product of C11-C15 linear secondary alcohol with 9 moles of ethylene oxide), Tergitol® 24-L- 6 NMW (the primary alcohol condensation product of C? -Cu with 6 moles of ethylene oxide with a limited molecular weight distribution), both distributed by Union Carbide Corporation; Neodol® 45-9 (the linear alcohol condensation product of Ci4 ~ Ci5 with 9 moles of ethylene oxide), Neodol® 23-6.5 (the linear alcohol condensation product of C? 2-C- | 3 with 6.5 moles of ethylene oxide), Neodol® 45.7 (the linear condensation product of C14-C15 with 7 moles of ethylene oxide), Neodol® 45.4 (the linear condensation product of C14-C15 with 4 moles of ethylene oxide), distributed by Shell Chemical Company, and Kyro® EOB (the condensation product of Ci3 ~ Ci5 alcohol with 9 moles of ethylene oxide), distributed by The Procter & amp;; Gamble Company. Other commercially available nonionic surfactants include Dobanol 91-8® distributed by Shell Chemical Co. and Genapol UD-080® distributed by Hoechst. This category of nonionic surfactant is generally referred to as "alkyl ethoxylates". The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds preferably has a molecular weight of about 1500 to about 1800 and exhibits insolubility in water. The addition of these polyoxyethylene portions to this hydrophobic portion tends to increase the water solubility in general and is retained in liquid character of the product to the extent that the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to the condensation up to approximately 40 moles of ethylene oxide. Mixtures of compounds of this type include some of the commercially available Pluronic® surfactants, distributed by BASF. The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic production of these products consists of the product of the action of ethylene diamine 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 product of The condensation contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 1 1,000. Examples of this type of nonionic surfactants include some of the commercially available Tetronic® compounds, distributed by BASF. Semi-polar nonionic surfactants are a special category of nonionic surfactants that include water-soluble amine oxides containing an alkyl portion of about 10 to about 18 carbon atoms and 2 portions selected from the group consisting of alkyl groups and groups hydroxyalkyl containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing an alkyl portion of about 10 to about 18 carbon atoms and 2 portions selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 about 3 carbon atoms; and water soluble sulfoxides containing an alkyl portion of about 10 to about 18 carbon atoms and a portion selected from a group consisting of alkyl and hydroxyalkyl portions of about 1 to about 3 carbon atoms. The semi-polar ionic detergent or surfactants include amine oxide surfactants having the formula wherein R3 is an alkyl, hydroxyalkyl or alkylphenyl group, or mixtures thereof, containing about 8 about 22 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing about 2 about 3 carbon atoms or mixtures thereof; x is 0 about 3; and each R 5 is an alkyl or hydroxyalkyl group containing about 1 about 3 carbon atoms or a polyethylene oxide group containing about 1 about 3 ethylene oxide groups. The R5 groups can be linked to one another, for example through oxygen or nitrogen atoms, to form an annular structure. These amine oxide surfactants include, in particular, alkyldimethylamine oxides of C-io-C-iß and oxides and alkoxyethyldihydroxyethylamine of C8-C? 2.

Alkylpolysaccharides disclosed in the U.S.A. 4,565,647, Filling, issued January 21, 1986, having a hydrophobic group containing from about 6 about 30 carbon atoms, preferably about 10 about 16 carbon atoms and a polysaccharide, for example a polyglycoside, hydrophilic group containing of about 1.3 about 10, preferably about 1.3 about 3, most preferably about 1.3 about 2.7 units of saccharide. Any reducing saccharide containing from 5 to 6 carbon atoms can be used, for example glucose, galactose and galactosyl portions can be substituted by glucosium portions (optionally it is joined by hydrophobic group in portions 2, 3, 4, etc., thus giving a glucose or galactose in contrast to a glucoside or galactoside). The linkages between the saccharides can be, for example, between a position of the additional saccharide units and positions 2, 3, 4 and / or 6 over the preceding units of saccharide. Optionally and less conveniently, there may be a polyalkylene oxide chain that binds the hydrophobic portion and the polysaccharide portion. The preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include alkyl groups, whether saturated and / or unsaturated, branched or unbranched, containing from about 8 about 18, preferably about 10 about 16, carbon atoms.

Preferably, the alkyl group is a saturated straight-chain alkyl group. The alkyl group can contain up to about 3 hydroxy groups and / or the polyalkylene oxide chain can contain up to about 10, preferably less than 5, alkylene oxide portions. Suitable alkyl polysaccharides are octyl, nonyl, decyl, undecyldecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructose , and / or galactoses. Suitable mixtures include coconut alkyl, di-, tri-, tetra- and pentaglucosides, and tallow alkyl tetra-, penta- and hexyl glucosides. Preferred alkyl polyglycosides have the formula R2O (CnH2nO) t (glycosyl) x wherein R2 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 from about 1.3 to about 3, most preferably from about 1.3 to about 2.7. the glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is first formed and then reacted with glucose, or a source of glucose to form the glucoside (linkage at position 1). The additional glycosyl units can then be joined between their 1- position and the 2-, 3-, 4- and / or 6- position of the preceding glycosyl units, preferably predominantly the 2-position. Amide surfactants of fatty acid having the formula: O R6-CN (R7) 2 wherein R6 is an alkyl group containing from about 7 to about 21 (preferably from about 9 to about 17) carbon atoms and each R7 is selected from the group consisting of hydrogen, CtC alkyl, hydroxyalkyl of C -? - C4 and - (C2H40) xH wherein x ranges from about 1 to about 3. Preferred amides are C8-C20 ammonia amides, monoethanolamides, diethanolamides, and isopropanolamides.

Cationic / amphoteric surfactant Non-quaternary cationic detersive surfactants may also be included in the detergent compositions of the present invention. Surfactants useful herein are described in the U.S.A. 4,228,044, Cambres, issued October 14, 1980. Ampholytic surfactants can be incorporated into the detergent compositions herein. These surfactants can be described in general terms as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary or tertiary amines in which the aliphatic radical can be straight or branched chain. One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water solubilizing group, for example carboxy, sulfonate, sulfate. See the patent of E.U.A. No. 3,929,678 to Laughiin et al., Issued December 30, 1975 in column 19, lines 18-35 for examples of ampholytic surfactants. Preferred amphoteric surfactants include alkyl ethoxylates ("AE") of C? 2-C? A, including so-called narrow peak alkyl ethoxylates and alkyl phenol C6-C? 2 alkoxylates (especially ethoxylates and mixed ethoxy / propoxy), betaines of C? -C? 8 and sulfobetaines ("sultaines") amine oxides of C? -C-is and mixtures thereof.

Polyhydroxy fatty acid amide surfactant The detergent compositions herein may also contain polyhydroxy fatty acid amide surfactant. The amide surfactant component polyhydroxy fatty acid comprise compounds of the structural formula: O R1 II I wherein: R1 is H, hydrocarbyl of C -? - C, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, preferably CrC alkyl, more preferably Ci or C2 alkyl, most preferably Ci alkyl ( that is, methyl); and R2 is a C-C3 hydrocarbyl, preferably straight-chain C7-C19 alkyl or alkenyl, more preferably straight-chain C9-C7 alkyl or alkenyl, more preferably straight-chain C11-C15 alkyl or alkenyl. , or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least three hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z will be preferably derived from a reducing sugar in a reductive amination reaction; more preferably Z will be glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. High-dextrose corn syrup, high-fructose corn syrup and high-maltose corn syrup, as well as the individual sugars listed above, can be used as starting materials. These corn syrups can provide a mixture of sugar components for Z. It should be understood that it is not intended in any way to exclude other suitable starting materials. Z will preferably be selected from the group consisting of -CH2- (CH0H) n-CH20H, -CH- (CH2OH) - (CHOH) n-1-CH2OH, -CH2- (CHOH) 2 (CHOR ') (CHOH) -CH2OH, and alkoxylated derivatives thereof, wherein n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide. Most preferred are glycityls wherein n is 4, particularly -CH2- (CHOH) 4-CH2OH.

R 'can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl, or N-2-hydroxypropyl. R2-CO-N < it can be, for example, cocoamide, stearamide, oleamide, lauramide, myristamide, capricamide, paimitamide, seboamide, etc. Z may be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactitiio, 1-deoxygalactityl, 1-deoxyanityl, 1-deoxymalototriotityl, etc. Methods for making polyhydroxy fatty acid amides are known in the art. In general, they can be made by reaction of an alkyl amine with a reducing sugar with a reductive amination reaction to form the corresponding N-alkyl polyhydroxyamine and then by reaction of the N-alkyl polyhydroxyamine with a fatty aliphatic ether or triglyceride in one step of condensation / amination to form the amide group of N-alkyl, N-polyhydroxy fatty acid. Methods for making compositions containing polyhydroxy fatty acid amides, for example, are set forth in the patent specification of G.B. 809,060, published February 18, 1959, by Thomas Hedley & Co., Ltd., the patent of E.U.A. 2,965,576, issued on December 20, 1960 to E.R. Wilson, and the patent E.U.A. 2,703,798, Anthony M. Schwartz, issued March 8, 1955, and patent of E.U.A. 1, 985,424, issued on December 25, 1934 to Piggott, each of which is incorporated herein by reference.

B. Granular and / or powder laundry detergent compositions Granular and / or powder laundry detergent compositions comprise, in addition to the enzyme granules of the present invention, one or more cleaning adjunct materials as described herein.

Cleaning Attachment Materials The laundry detergent compositions of the present invention as described hereinbefore may optionally include, in addition to the enzyme granules of the present invention, cleaning adjunct materials described below.

Biodegradable Branched Surfactants The present invention includes important embodiments comprising at least one surfactant or a mixture of biodegradable branched and / or decomposed by crystallinity and / or branched half-chain surfactants. The terms "biodegradablely branched" and / or "decomposed in crystallinity" and / or "branched to half chain" (acronym "MCB" used hereafter "indicates that such surfactants or mixtures of surfactants are characterized by the the presence of surfactant molecules having a moderately non-linear hydrophobe, more particularly, in that the hydrophobic surfactant is not completely linear, on the one hand, nor is it branched to a degree that would result in unacceptable degradation.The preferred biodegradable branched surfactants are different from the known commercial types LAS, ABS, Exxal, Lial, etc., either branched or unbranched The materials biodegradable comprise particularly positioned light branching, for example of about 1 about 3 methyl and / or ethyl and / or propyl branches and / or butyl in the hydrophobe, in which the branch is located remotely from the main group of surfactant, preferably towards the center of the hydrophobe. Typically, one to three such branches may be present on a single hydrophobe, preferably only one. Such biodegradable branched surfactants may have exclusively linear aliphatic hydrophobes or hydrophobes may include cycloaliphatic or aromatic substitution. The MCB analogs of common linear alkyl sulphate, linear alkyl alkoxylate and linear alkylbenzene sulfonate surfactants are preferred to a single degree, said surfactant being suitably selected from C8-C alkylsulfates with half-chain branching (Ca-alkyl). ds) ethoxylated alcohols, propoxylated or butoxylated with branches of C -? - C4 at half chain, (C8-C18 alkyl) ethoxysulfates with ramifications of CrC at half chain, (C8-C8 alkyl) benzenesulfonates with ramifications of C? -C a half chain and mixtures thereof. When they are anionic, the surfactants can be in general in the form of an acid or a salt, for example sodium, potassium, ammonium and substituted ammonium. The biodegradable branched surfactants offer substantial improvements in cleaning performance and / or utility in cold water and / or water hardness and / or economy of use. Such surfactants may, in general, belong to any known class of surfactants, for example anionic, nonionic, cationic and zwitterionic agents. The biodegradable branched surfactants are synthesized by Procter & amp;; Gamble, Shell and Sasol. These surfactants are described in more detail in documents W098 / 23712 A published 04/06/98; W097 / 38957 A published on 10/23/97; W097 / 38956 A published on 10/23/97; WO97 / 39091 published 10/23/97; WO97 / 39089 A published on 10/23/97; WO97 / 39088 A published on 10/23/97; WO97 / 39087 A1 published on 10/23/97; W097 / 38972 A published on 10/23/97; WO 98/23566 A Shell, published 04/06/98; Sasol's technical bulletins; and the following pending patent applications assigned to Procter & Gamble: Preferred biodegradable branched surfactants herein include MCB surfactants, as disclosed in the following references: W098 / 23712 A published on 06/04/98 includes an exposure of non-ionic surfactants MCB, including alkyl polyoxyalkylene primate MCB of the formula (I): CH3CH2 (CH2) wC (R) H (CH2) xC (R1) H (CH2) and C (R2) H (CH2) z (EO / PO) mOH (I), in which the total number of carbon atoms in the The primary branched alkyl portion of this formula, including the branching of R, R1 and R2, but not including the carbon atoms of the EO / PO alkoxy moiety, is preferably 14-20, in which addition to this mixture of agents surfactants, the average total number of carbon atoms in the hydrophobic portion of primary alkyl MCB is preferably 14.5-17.5, more preferably 15-17; each of R, R1 and R2 is independently selected from hydrogen and C1-C3 alkyl, preferably methyl, provided that R, R1 and R2 are not both hydrogen and, when z is 1, at least R or R1 is not it is hydrogen; w is an integer of 0-13; x is an integer number O-13; is an integer of 0-13; z is an integer of at least 1; w + x + y + z equals 8-14; and EO / PO are alkoxy portions preferably selected from mixed ethoxy, propoxy and ethoxy / propoxy groups, wherein m is at least 1, preferably 3-30, more preferably 5-20, most preferably 5-15. Such nonionic surfactants MCB may alternatively include portions derived from butylene oxide and the -OH portion may be replaced by any of the well known ends blocking portions that are used for conventional nonionic surfactants. The document W097 / 38957 A published on 10/23/97 includes the exposure of branched alcohols to half chain or almost half chain of the formulas R-CH2CH2CH (Me) CH-R1-CH2OH (I) and HOCH2R-CH2-CH2 -CH (Me) -R '(II) comprising: (A) dimerizing alpha-olefins of the formula RCH = CH2 and R1CH = CH2 to form olefins of the formula R (CH2) -C (R1) = CH2 and R1 (CH2) 2-C (R) = CH2; (B) (i) isomerizing the olefins and then reacting them with carbon monoxide and hydrogen under Oxo conditions (i) directly reacting the olefins of step (A) with CO / H under Oxo conditions. In the above formulas, R, R1 = a linear alkyl of C3-C7. W097 / 38957 also discloses (i) sulphonting sulfate (I) or (II) surfactant surfactants; (ii) alkylene-sulfate MCB preparation comprising ethoxylating and then sulfating (I) or (II); (iii) preparation of surfactants and alkylcarboxylate MSB comprising (I) or (II) or their aldehyde intermediates and (iv) preparation of surfactants acyltaurate, acyl isothiorate MCB, acyl sarcosinate MBS or acyl-N-methylglucamide MSB, using the alkyl branched carboxylates as a supply material. Document W097 / 38956 A published on 10/23/97 discloses the preparation of branched alpha-olefins at half chain or almost half a chain that are carried out: (a) by preparing a mixture of carbon monoxide and hydrogen; (b) reacting the mixture in the presence of a catalyst under Fischer-Tropsch conditions to prepare a mixture of hydrocarbons comprising the described olefins; and (c) separating the olefins from the hydrocarbon mixture. The document W097 / 38956 A also discloses the preparation of branched alcohols at half chain or almost half chain by reacting the described olefins with CO / H2 under oxo conditions. These alcohols can be used to prepare (1) MCB sulfate surfactants, sulfating the alcohols; (2) alkyl ethoxy sulphates MSB, ethoxylating, then sulfating, the alcohols: or (3) branched alkyl carboxylate surfactants, oxidizing the alcohols or their aldehyde intermediates. The branched carboxylates formed as a supply material can be used to prepare surfactants of acyltaurate, acyl isethionate, acyl sarcosinate, or acyl-N-methylglucamide, etc. WO97 / 39091 A published on 10/23/97 includes the exposure of a detergent surfactant composition comprising at least 0.5 (especially 5, more especially 10, most especially 20) wt% longer alkyl chain, agent MSB surfactant of the formula (I), AXB (I) wherein A is an alkyl hydrophobe MSB of 9-22 (especially 12-18) C having: (i) the longest linear C chain attached to the portion XB of 8-21 C atoms; (ii) 1-3C alkyl portions branching from their longest linear chain; (iii) at least one of the branching alkyl portions directly attached C of the longest linear C chain at a position within the range of the C2 position, contact starting from 1 which is attached to the CH2B portion, at omega-2 carbon (the C-terminal minus 2C); and (v) the surfactant composition has a mean total number of C atoms in the A-X portion of 14.5-17.5 (especially 15-17); and B is a hydrophilic portion (main surfactant group) preferably selected from sulfates, sulphonates, polyoxyalkylene, (especially polyoxyethylene or polyoxypropylene), alkoxylated sulfates, polyhydroxy portions, phosphate esters, glycerol sulfonates, polygluconates, polyphosphates-esters, phosphonate, sulfosuccinates , polyalcohoxylated carboxylates, glucamides, taurinates, sarcosinates, glycinates, isethionates, mono- / di-alkanol-amides, monoalkanolamide sulphates, diglycolamide and its sulfates, glyceryl esters and their sulfates, glycerol ethers and their sulfates, polyglycerol ether and their sulfates, sorbitan esters, polyalkoxylated sorbitan esters, ammonium alkane sulphonates, amidopropyl betaines, alkylated quaternary ammonium, alkylated quaternary ammonium / polyhydroxyalkylated ammonium, imidazolines, 2-yl succinates, sulfonated alkylesters and sulfonated fatty acids; and X is -CH2- or -C (O) -, WO97 / 39091 A also exposes a laundry detergent or other cleaning composition comprising: (a) 0.001-99% detergent surfactant (I); and (b) 1-99.99% of the attached ingredients. WO97 / 39089 A published on 10/23/97 includes the disclosure of liquid cleaning compositions comprising: (a) as part of a surfactant system 0.1-50 (especially 1-40)% by weight of branched surfactant a half chain of the formula (I); (b) as the other part of the surfactant system 0.1-50% by weight surfactant coagents; (c) 1-99.7% by weight of a solvent; and (d) 0.1-75% by weight of adjunct ingredients. The formula (I) is A-CH2-B in which A = 9-22 (especially 12-18) C of alkyl hydrophobe MCB having: (i) the longest linear C chain attached to the XB portion of 8 -21 C atoms; (ii) 1-3C alkyl portions branching from this longer linear chain; (iii) at least one of the branched alkyl portions attached directly to a C of the longest linear C chain at a position within the range of the 2 C position, counting from carbon No. 1 which is attached to the CH2B portion, to the omega-2 carbon (the C-terminal minus 2C); and (v) the surfactant composition has a mean total number of C atoms in the A-X portion of 14.5-17.5 (especially 15-17); and B is a hydrophilic portion selected from sulfates, polyoxyalkylene (especially polyoxyethylene and polyoxypropylene) and alkoxylated sulfates. WO97 / 39088 A published 10/23/97 includes exposure to a surfactant composition comprising 0.001-100% alkoxylated sulfates and primary alkyl MCB of the formula (I): CH3CH2 (CH) wCHR (CH2)? CHR1 ( CH2) and CHR2 (CH2) zOS03M (I) in which the total number of C atoms in the compound (I) including R, R1, and R2, is preferably 14-20 and the total number of C atoms in the portions of branched alkyl is on average preferably 14.5-17.5 (especially 15-17); R, R1 and R2 are selected from H and alkyl of 1-3 C (especially Me) provided that R, R1, and R2 are not both H; when z = 1, at least R or R1 is not H; M are cations selected especially from Na, K, Ca, Mg, alkyl quaternary ammonium of the formula N + R3R4R5R6 (II); M is especially Na and / or K; R3, R4, R5, R6 are selected from H, alkylene of 1-22C, branched alkylene of 4-22C, alkanol of 1-6C, alkenylene of 1-22C and / or branched alkylene of 4-22C; w, x, y = 0-13; z is at least 1; w + x + y + z = 8-14. WO97 / 39088 A also discloses (1) a surfactant composition comprising a mixture of branched primary alkyl sulphates of the formula (I) as mentioned above. M is a water-soluble cation; when R2 is alkyl of 1-3C, the ratio of the surfactants having z = 2 or more is preferably at least 1: 1 (most especially 1: 100); (2) a detergent composition comprising: (a) 0.001-99% alkoxylated primary alkyl sulphate MCB of the formulas (III) and / or (IV) CH3 (CH2) aCH (CH3) (CH2) bCH2OS03M (III) , CH3 (CH2) dCH (CH3) (CH2) eCH (CH3) CH2OS03M (IV), in which a, b, d, and e are pure integers, preferably a + b = 10-16, df = 8-14 y, when a + b = 10, a 2-9 and b = 1-8; when a + b = 11, a = 2-10 and b = 1-9, when a + b = 12, a = 2-11 and b = 1-10 when a + b = 13, a = 2-12 and b = 1 -eleven; when a + b = 14, a = 2-13 and b = 1-12, when a + b = 15, a = 2-14 and b = 1-13; when a + b = 16, a = 2-14 and b = 1-4; when d + e = 8, d = 2-7 and e = 1-6; when d + e = 9, d = 2-8 and e = 1-7 when d + e = 10, d = 2-9 and e = 1-8; when d + e = 11, d = 2-10 and e = 1-9 when d + e = 12, d = 2-11 and e = 1-10; when d + e = 13, d = 2-12 and e = 1-11 when d + e = 14, d = 2-13 and e = 1-12; and (b) 1-99.99 by weight% of detergent adjuncts; (3) a medium chain branched alkyl sulfate surfactant of the formula (V): CH3 (CH2) xCHR1 (CH2) and CHR2 (CH2) zOS03M (V), wherein x, y = 0-12; z is at least 2; x + y + z = 11-14; R1 and R2 are not both H; when one of R1 or R2 is H, and the other is Me, x + and z is not 12 or 13; and when R1 is H and R2 is Me, x + y is not 11 when z = 3 and x + y is not 9 when z = 5; (4) alkyl sulphates of the formula (III) in which a and b are integers and a = b = 12 or 13, a = 2-11, b = 1-10 and M is Na, K, and optionally substituted ammonium; (5) alkyl sulfates of the formula (IV) in which d and e are integers and d = e is 10 or 11 and when d = e is 10, d = 2-9 and e = 1-8; when d = 3 = 11, d = 2-10 and e = 1-9 and m is Na, K, optionally substituted ammonium (especially Na); (6) branched alkyl primary sulfates with methyl selected from 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12- or 13-methylpentadecanolsulfate; 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 1-, 12-, 13-, or 14-methylhexadecanolsulfate; 2,3-, 2,4-, 2,5-, 1, 6-, 2,7-, 2,8-, 2,9-, 2,10-, 2,1-, 2,12- methytetradecanolsulfate; 2,3-, 2,4-, 2,5-, 1, 6-, 2,7-, 2,8-, 2,9-, 2,10-, 2,1-, 2,12- , or 2,13-methylpentadecanolsulfate and / or mixtures of these compounds. WO97 / 39087 A published on 10/23/97 includes the surfactant composition comprising 0.001-100% alkoxylated sulfates of branched primary alkyl the half chain of formula (I) in which the total number of C atoms in the compound (1) including R, R1 and R3, but not including the C atoms of the EO / PO alkoxy portions is 14-20 and the total number of C atoms in the branched alkyl portions is on average 14.5- 17.5 (especially 15-17); R, R1 and R2 = H or alkyl of 1-3C (especially Me) and R, R1 and R2 are not both H; when z equal to 1 at least R or R1 are not H; M = cations selected especially among Na, K, Ca, Mg, alkyl quaternary amines of the formula (II) (M is especially Na and / or K) R3, R4, R5, R6 = H, alkylene of 1 -22 C, alkylene 4-22C branched, 1-6C alkanol, 1-22C alkenylene and / or branched alkenylene of 4-22C; w, x, y = 0.13; z is at least 1; w + x + y + z = 8-14; EO / PO are alkoxy portions, especially ethoxy and / or propoxy; m is at least 0.01, especially 0.1 -30, more especially 0.5-10, very especially 1-5. Also disclosed are: (1) a surfactant composition comprising a mixture of branched alkyl primary alkoxylated sulfates of the formula (I). When R2 = alkyl of 1-3C, the ratio of surfactants having z = 2 or greater to the surfactant having z = 1 is at least 1: 1, especially 1.5: 1, more especially 3: 1, very especially 4: 1; (2) a detergent composition comprising: (a) 0.001-99% alkoxylated primary alkyl sulphate branched to the half chain of the formula (III) and / or (IV); M is as mentioned above; a, b, d and e are integers, a + b = 10-16, dé = 8-14 and, when a + b = 10, a 2-9 and b = 1-8; when a + b = 11, a = 2-10 and b = 1-9, when a + b = 12, a = 2-11 and b = 1-10 when a + b = 13, a = 2-12 and b = 1 -eleven; when a + b = 14, a = 2-13 and b = 1-12, when a + b = 15, a = 2-14 and b = 1-13; when a + b = 16, a = 2-14 and b = 1-4; when d + e = 8, d = 2-7 and e = 1-6; when d + e = 9, d = 2-8 and e = 1-7 when d + e = 10, d = 2-9 and e = 1-8; when d + e = 11, d = 2-10 and e = 1-9 when d + e = 12, d = 2-11 and e = 1-10; when d + e = 13, d = 2-12 and e = 1-11 when d + e = 14, d = 2-13 and e = 1-12; and (b) 1-99.99 by weight% of detergent adjuncts; (3) a medium chain branched alkyl sulfate surfactant of the formula (V): R1, R2, M, EO / PO, m as previously indicated; x, y = 0-12; z is at least 2; x + y + z equal to 11-14; (4) an alkoxylated alkyl sulfate branched to half chain of the formula (III) in which: a = 2-11; b = 1-10; a + b = 12 or 13; M, EO / PO and m is as indicated above; (5) an alkoxylated sulfate and branched chain alkyl alkyl compound of the formula (IV) in which: d + c = 10 or 11; when d + e = 10, d = 2-9 and e = 1-8 and when d + e = 11, d = 2-10 and e = 1-9; M is as indicated above (especially Na); EO / PO and m are as indicated above; and (6) ethoxylated primary alkyl branched alkyl sulfates with methyl selected from 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12- or 13-methylpentadecanolsulfate; 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, or 14-methylhexadecanolsulfate; 2,3-, 2,4-, 2,5-, 1, 6-, 2,7-, 2,8-, 2,9-, 2,10-, 2,11-, 2,12- methyltetradecanolsulfate; 2,3-, 2,4-, 2,5-, 1, 6-, 2,7-, 2,8-, 2,9-, 2,10-, 2,11-, 2,12-, or 2,13-ethoxylated methylpentadecanolsulfate and / or mixtures of these compounds. These compounds are ethoxylated with an average degree of ethoxylation of 0.1-10. W097 / 38972 A published on 10/23/97 includes the disclosure of a method for making compositions in mixtures of longer chain alkyl sulfate surfactants comprising (a) sulfating with S03, preferably in a falling film reactor, a mixture of long-chain aliphatic alcohols having an average carbon chain length of at least 14.5-17.5, the mixture of alcohols comprising at least 10%, preferably at least 25% more preferably at least 50%, more preferably still at least 75%, most preferably at least 95% of an aliphatic alcohol MCB having the formula (I); wherein: R, R1, R2 = H or alkyl of 1-3C, preferably methyl, provided that R, R1 and R2 are not both H, and when z = 1, at least R or R1 is not H; w, x, y = to the integers 0-13; z equal to integer at least 1; w + x + y + z = 8-14; in which the total number of carbon atoms in the primary and branched alkyl position of the formula (II), including the branching of R, R1 and R2, is 14-20, in which in addition to the alcohol mixture the number average total of carbon atoms in the branched primary alkyl portions having the formula (I) is > 14.5-17.5, preferably, > 15-17; and (b) neutralizing the alkyl sulfate acid produced in step (a), preferably using a base selected from KOH, NaOH, ammonia, monoethanolamine, triethanolamine and mixtures thereof. Also disclosed is a method for making compositions of alkoxylated sulfate surfactant mixtures of longer chain alkyls comprising alkoxylating the specified mixture of long chain aliphatic alcohols; sulfating the resulting polysialkylene alcohol with S03; and neutralizing the resulting alkyl alkoxylated sulfate. Alternatively, the alkoxylated alkyl sulphates can be produced directly from the polyoxyalkylene alcohol, S03 sulfate and neutralizing. WO 98/23566 A Shell, published 06/04/98 discloses branched primary alcohol compositions having 8-36 C atoms and an average number of branches per mole of 0.7-3 and comprising ethyl and methyl branches. Also disclosed are: (1) a branched primary alkoxylate composition which can be prepared by reacting a branched primary alcohol composition as mentioned above with an oxirane compound; (2) a branched primary alcohol sulfate which can be prepared by sulfating a primary alcohol composition as mentioned above; (3) a branched alkoxylated primary alcohol sulfate which can be prepared, alkoxylating and sulfating a branched alcohol composition as mentioned above; (4) a branched primary alcohol carboxylate which can be prepared by oxidizing a branched primary alcohol composition as mentioned above; (5) a detergent composition comprising: (a) surfactants selected from the alkoxylates of branched primary alcohol as in (1), branched primary alcohol sulfate as in (2) and branched alkoxylated primary alcohol sulfates as in (3); (b) a detergency builder; and (c) optionally additives selected from foam control agents, enzymes, bleaching agents, bleach activators, optical brighteners, or with builders, hydrotropes and stabilizers. The primary alcohol composition and the sulfates, alkoxylates, alkoxy sulfates and carboxylates prepared therefrom exhibit good detergency and biodegradability in cold water. The biodegradable branched surfactants useful herein also include the modified alkylaromatic surfactants, especially modified alkylbenzene sulfonate surfactants described in commonly assigned co-pending patent applications (case numbers from P &G, 7303P, 7304P). In more detail, these surfactants include (cases of P & G 6766P) alkylarylsulfonate surfactant systems comprising from about 10% to about 100% by weight of said surfactant system of two or more alkylarylsulfonate surfactants decomposed in their crystallinity. the formula (B-Ar-D) a (Mq +) b in which D is S03", M is a cation or mixtures of cations, q is the valence of said cation, a and b are numbers selected in such a way that said composition is electroneutro Ar is selected from benzene, toluene and combinations thereof, and B comprises the sum of at least one portion of primary hydrocarbyl containing 5 to 20 carbon atoms and one or more portions of decomposition in the crystallinity in which said decomposition portions in the crystallinity are interrupted or branched from said hydrocarbyl portion; and that said alkylarylsulfonate surfactant system has the composition in crystallinity to the extent that its critical sodium solubility temperature, as measured by the CST test, is not more than about 40 ° C and that in addition said alkylarylsulfonate surfactant system has at least one of the following properties: percentage biodegradation, as measured by the modified SCAS test, which exceeds tetrapropylenebenzene sulfonate; and weight ratio of the non-quaternary and quaternary carbon atoms and B at least about 5: 1. Such compositions also include (cases of P &G 7303P) mixtures of surfactants comprising (preferably, consisting essentially of): (a) from about 60% to about 95% by weight (preferably from about 65% to about 90%) , more preferably from about 70% to about 85%) of a mixture of branched alkylbenzene sulfonates having the formula (I): (I) in which 'L is an acyclic aliphatic portion consisting of carbon and hydrogen and having two methyl terminals, wherein said mixture of branched alkylbenzene sulfonates contains two or more (preferably at least three, optionally more) of said compounds which differ in molecular weight from the anion of said formula (I) and wherein said mixture of branched alkylbenzene sulphonates is characterized by an average carbon content of about 10.0 to about 14.0 carbon atoms (preferably from about 11.0 to about 13.0, more preferably about 11.5 to about 12.5), wherein said average carbon content is based on the sum of carbon atoms in R1, L and R2 (preferably said sum of carbon atoms in R1, L and R2 is from 9 to 15, more preferably from 10 to 14), and further, in that L has no substituents in addition to A, R1 and R2; M is a cation or mixture of - cations (preferably selected from H, Na, K, Ca, Mg and mixtures thereof, most preferably selected from H, Na, and mixtures thereof, most preferably even selected from H, Na and mixtures thereof) it has a valence q (typically 1 to 2, preferably 1); a and b are selected integers such that such compounds are electroneutral (a is typically 1 to 2, preferably 1, b is 1); R1 is C1-C3 alkyl (preferably C1-C2 alkyl, more preferably methyl); R 2 is selected from H and C 1 -C 3 alkyl (preferably H and C 1 -C 2 alkyl, more preferably H and methyl, more preferably H and methyl provided that at least about 0.5, more preferably 0.7, more preferably 0.9 to 1.0 mole fraction of said branched alkylbenzene sulphonates R2 is H); A is a benzene portion (typically A is the -CeH4- portion, with the S03 portion of the formula (I) in the para portion to the L portion, although in a certain portion, usually not more than about 5%, preferably from 0 to 5% by weight, portion S03 is ortho to L); and (b) from about 5% to about 60% by weight (preferably from about 10% to about 35%, more preferably from about 15% to about 30%) of a mixture of unbranched alkylbenzene sulphonates having the formula (II) :? Y IA [Mq?] B S03 a (II) in which a, b, M, A and q are as defined above in the present and Y is an unsubstituted linear aliphatic portion consisting of carbon and hydrogen having two methyl terminals , wherein Y has an average carbon content of about 10.0 to about 14.0 (preferably about 1.0 to about 13.0, more preferably 11.5 to 12.5 carbon atoms); (preferably said mixture of unbranched alkylbenzene sulphonates is further characterized by a sum of carbon atoms in Y from 9 to 15, more preferably from 10 to 14); and wherein said composition is further characterized by an index of 2/3 phenyls of from about 350 to about 10,000 (preferably from about 400 to about 1,200, more preferably from about 500 to about 700) (and also preferably in that said mixture of agents surfactants have a 2-methyl-2-phenyl index of less than about 0.3, preferably less than about 0.2, more preferably less than about 0.1, more preferably still from 0 to 0.05). Also covered through the medium chain branched surfactants of the alkylbenzene derivative types are mixtures of surfactants comprising a product of a process comprising the steps of: alkylating benzene with an alkylation mixture; sulfonate the product of (I); and neutralizing the product of (II); wherein said alkylation mixture comprises: (a) from about 1% to about 99.9%, by weight of the branched C7-C2o monoolefins, said branched monoolefins having structures identical to those of the branched monoolefins which are formed by dehydrogenating branched paraffins of the formula R1LR2 in which L is an acyclic aliphatic portion consisting of carbon and hydrogen and containing two terminal methyls; R 1 is C 1 to C 3 alkyl; and R2 is selected from H and Ci to C3; and (b) from about 0.1% to about 85%, by weight of linear C7-C20 aliphatic olefins; wherein said alkylation mixture contains said branched C7-C2o monoolefins having at least two different carbon numbers in said range of C7-C20 and has an average carbon content of about 9.5 to about 14.5 carbon atoms; and wherein said components (a) and (b) are in the weight ratio of at least about 15:85.

Bleaching system The laundry compositions of the present invention may comprise a bleaching system. Bleaching systems typically comprise a "bleaching agent" (source of hydrogen peroxide) and an "initiator" or "catalyst". When present, bleaching agents will typically be at levels of about 1%, preferably from about 5% to about 30%, preferably about 20% by weight of the composition. If present, the amount of bleach activator will typically be about 0.1%, preferably from about 0.5% to about 60%, preferably about 40%, by weight of the bleaching composition comprising the bleaching agent plus the bleach activator.

Bleaching agents The sources of hydrogen peroxide are described in detail in Kirk Othmer Encyclopedia of Chemical Technology, 4th Ed. (1992, John Wiley & Sons), Vol. 4, pgs. 271-300"Bleaching Agents (Survey)", incorporated herein, and the same include the various forms of sodium perborate and sodium percarbonate, including various coated and modified forms. The preferred source of hydrogen peroxide used herein may be any convenient source, including hydrogen peroxide itself. For example, perborate, for example sodium perborate (hydrate in general, but preferably mono- or tetrahydrate), sodium carbonate peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate or sodium peroxide can be used in the present perborate. Sources of obtainable oxygen, such as persulfate bleach (e.g. OXONE, manufactured by DuPont) are also useful. Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of any convenient sources of hydrogen peroxide can also be used. A preferred percarbonate bleach comprises dry particles having an average particle size in the range of about 500 microns to about 1,000 microns, with no more than about 10% by weight of said particles being smaller than about 200 microns and being not more than about 10% by weight of said particles larger than about 1.250 microns. Optionally, the percarbonate can be coated with a silicate, borate or water-soluble surfactants. The percarbonate is obtainable from various commercial sources, such as FMC, Solvay and Tokai Denka. The compositions of the present invention may also comprise as the bleaching agent a chlorine-type bleaching material. Such agents are well known in the art includes for example sodium dichloroisocyanurate ("NaDCC"). However, chlorine-type bleaches are less preferred for compositions comprising enzymes. (a) Blanking activators Preferably, the peroxygen bleaching component in the composition is formulated with an activator (peracid precursor). The activator is present at levels of about 0.01%, preferably about 0.5%, more preferably from about 1% to about 15%, preferably about 10%, more preferably about 8%, by weight of the composition. Preferred activators are selected from the group consisting of tetraacetylethylenediamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulfonate (BOBS), nonanoyloxybenzenesulfonate (NOBS), phenylbenzoate (PhBz), decanoyloxybenzenesulfonate (C ^ -OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulfonate (C8-OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulfonate (C8-OBS), perhydrolyzable esters and mixtures thereof, most preferably benzoylcaprolactam and bezoylvalerolactam. Particularly preferred bleach activators in the pH range of about 8 to about 9.5 are those selected having an OBS or VL output group. Preferred hydrophobic bleach activators include, but are not limited thereto, nonanoyloxybenzenesulfonate (NOBS), salt of 4- [N- (nonaoyl) aminohexanoyloxy] -benzenesulfonate (NACA-OBS) an example of which is described in the patent of E.U.A. No. 5,523,434, dodecanoyloxybenzenesulfonate (LOBS or C? 2-OBS), 10-undecenoyloxybenzenesulfonate (UDOBS O C-p-OBA with 10-position unsaturation) and decanoyloxybenzoic acid (DOBA). Preferred bleach activators are those described in the U.S. Patents. 5,698,504, Christie et al., Issued December 16, 1997; 5,695,679, Christie et al., Issued December 9, 1997, 5,686,401, Willey et al., Issued November 11, 1997; 5,686,014, Hartshom et al., Issued November 11, 1997; 5,405,412, Willey et al., Issued April 11, 1995; 5,405,413, Willey et al., Issued April 11, 1995, 5,130,045, Mitchel et al., Issued July 14, 1992; and 4,412,934, Chung et al., issued November 1, 1983, and the co-pending patent applications of US. Serial No. Nos. 08 / 709,072, 08 / 064,564, all of which are incorporated herein by reference. The molar ratio of the peroxygen bleach compound (as AvO) the bleach activator in the present invention generally varies from at least 1: 1, preferably from approximately 20: 1, more preferably from approximately 10: 1 to approximately 1: 1, preferably to approximately 3: 1. Quarternary substituted bleach activators may also be included. The present laundry compositions preferably comprise a quaternary substituted bleach activator (QSBA) or a substituted quaternary peracid (QSP); more preferably, the first. Preferred structures of QSBA are also described in the U.S.A. 5,686,015 Willey et al., Issued November 11, 1997; 5,654,421, Taylor et al., Issued Aug. 5, 1997, 5,460,747, Gosselink et al., Issued October 24, 1995, 5,584,888, Miracle et al., Issued December 17, 1996; and 5,578,136, Taylor et al., issued November 26, 1996; all of which are incorporated herein by reference. Highly preferred bleach activators useful herein are amine-substituted, as described in the U.S. Patents. 5,698,504, 5,695,679 and 5,686,014 each of which is cited hereinbefore. Preferred examples of such bleach activators include: (6-octanamidocaproyl) oxybenzenesulfonate, (6-nonanamido-caproyl) oxybenzenesulfonate (6-decanamidocaproyl) oxybenzenesulfonate and mixtures thereof. Other useful activators, set forth in the patents of E.U.A. 5,698,504, 5,695,679, 5,686,014, each of which is cited hereinabove and the patent of E.U.A. 4,966,723, Hodge et al., Issued October 30, 1990, including benzoxacin activators, such as a C6H ring to which a portion -C (0) OC (R1) = N is fused at positions 1, 2 -. Depending on the activator and the precise application, good bleaching results can be obtained from bleaching systems having in use a pH of from about 6 to about 13, preferably from about 9.0 to about 10.5. Typically, for example, activators with electron withdrawing portions are used for near-neutral or sub-neutral pH ranges. Alkalis and pH regulating agents can be used to ensure such a pH. Lactam activators, as described in the U.S.A. 5,698,504, 5,695,679 and 5,586,014, each of which is cited hereinabove, are very useful herein, especially the acylcaprolactams (see for example WO 94-28102 A) and the acylvalerolactams (see U.S. Patent 5,503,639 Willey et al., Issued April 2, 1996, incorporated herein by reference). (b) Organic peroxides, especially diacylperoxides These are illustrated extensively in Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 17, John Wiley and Sons, 1982 on pages 27-90 and especially on pages 63-72, all incorporated in the present by reference. If a diacylperoxide is used, preferably one is given which exerts minimal adverse impact on the formation of spots and films.

Metal containing bleach catalysts The compositions and methods of the present invention can utilize bleach catalysts which contain in metal and which are effective for use in bleaching compositions. Bleach catalysts containing manganese and comal are preferred. One type of metal-containing bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cations, a cation of auxiliary metal having little or no catalytic bleaching activity, such as zinc or aluminum cations, and a sequestered cation having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetramethylene phosphonic acid and soluble salts thereof. water of them. Such catalysts are disclosed in the US patent. 4,430,243 Bragg, issued February 2, 1982.

Manganese metal complexes If desired, the compositions herein can be catalyzed by means of a manganese compound. Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts set forth in the U.S. Patents. Nos. 5,576,282, 5,246,621, 5,244,594, and 5,114,606; and European patent application publications Nos. 549,271 A1, 549,272 A1, 544,440 A2, and 544,490 A1; Preferred examples of these catalysts include Mnlv2 (u-0) 3 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2 (PF6) 2, Mn, M2 (u-0) 1 (u-OAc ) 2 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2 (Cl 4) 2, MnIV 4 (u-0) 6 (1, 4,7-triazacyclononane) 4 (CI04) 4, Mn "'" Mnlv4 (u-0) 1 (u-OAc) 2- (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2 (CI04) 3) Mn? V ( 1, 4,7-t4-trimethyl-1, 4,7-triazaclononano9- (OCH3) 3 (PF6), and mixtures thereof Other metal-based bleach catalysts include those set forth in U.S. Patent Nos. 4,430,243 and US 5,114.61 1. The use of manganese with several complex ligands to enhance bleaching is also reported in the following US Patents Nos. 4,728,455, 5,284,944, 5,246,612, 5,256,799, 5,280,117, 5,274,147, 5,153,161, and 5,227,084.

Cobalt Metal Complexes Cobalt catalysts useful herein are known and described, for example, in the U.S. Patents. Nos. 5,597,936, 5,595,967, and 5,703,030; and M.L. Tobe, "Base Hydrolysis of Transition Metal Complexes", Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1-94. More preferred cobalt catalysts useful herein are salts of cobalt-pentamine acetate having the formula [Co (NH3) 5 OAc] Ty, in which "OAc" represents an acetate portion and "Ty" is an anion, and especially cobalt-pentaamine acetate-acetate, [Co (NH3) 5 OAc] CI2; as well as [Co (NH3) 5 OAc] (OAc) 2; [Co (NH3) 5 OAc] (PF6) 2; [Co (NH3) 5 OAc] (S04); [Co (NH3) 5 OAc] (BF4) 2; and [Co (NH3) 5 OAc] (N03) 2 (in the present "CAP"). These cobalt catalysts are easily prepared by known methods, as taught for example in the U.S. Patents. Nos. 5,597,936, 5,595,967, and 5,703,030; in Tobe's article and the references cited therein; and in the patent of E.U.A. 4,810,410; 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, 1497-1502 (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).

Transition metal complexes of macropolycyclic rigid ligands The compositions herein may suitably include as a bleach catalyst a transition metal complex of a rigid macropolyclic ligand. The phrase "macropolicíclico rigid ligand" is sometimes abbreviated as "MRL" in the following discussion. The amount used is a catalytically effective amount, suitably from about 1 ppb or more, for example up to about 99.9%, more typically from about 0.001 ppm or more, preferably from about 0.05 ppm to about 500 ppm (in which "ppb" denotes parts per billion in weight "ppm" denotes parts per billion in weight). Suitable transition metals, for example Mn., Are illustrated below. "macropolicíclico" means an MRL and is a macrocycle and is polycyclic at the same time. "Polycyclic" means at least bicyclic. The term "rigid" as used herein includes "having a superstructure" and "cross-bridging." "Rigid" has been defined as the restricted inverse of flexibility: see D.H. Busch., Chemical Reviews., (1993) incorporated by reference. More particularly, "rigid" as used herein means that the MRL must be more rigid determinant than a macrocycle ("macrocycle of origin") that is otherwise identical (having the same ring size and type and number of atoms). in the main ring), but lacking a superstructure (especially link portions or preferably cross-bridged portions) found in the RMLs. In determining the comparative stiffness of macrocycles with or without structures, the skilled person will use the free form (not the metal-bound form) of macrocycles. It is well known that rigidity is useful when comparing macrocycles; Suitable tools for determining, measuring or comparing stiffness include computational methods (see, for example, Zimmer, Chemical Reviews, (1995), 95 (38), 2629-2648 or Hancock et al., Inorganic Chimica Acta, (1989) , 164, 73-84). Preferred MRLs herein are of the special type of ligand or rigid which is cross-bridged. A "cross bridge" is illustrated in a non-limiting manner in formula 3 below in the present. In formula 3, the cross bridge is a portion -CH2CH2-. Bridge to N1 and N8 in the illustrative structure. By comparison, a bridge "on the same side", for example if it were to be introduced through N1 and N2 in formula 3, would not be enough to constitute a "cross bridge" and therefore would not be preferred. Suitable metals in rigid ligand complexes include Mn (il), Mn (lll), Mn (IV), Mn (V), Fe (ll), Fe (lll), Fe (IV), Co (l), Co (ll), Co (III), Ni (l), Ni (ll), Ni (lll), Cu (l), Cu (ll), Cu (lll), Cr (ll), Cr (lll), Cr (IV), Cr (V), Cr (VI), V (lll), V (IV), V (V), Mo (IV), Mo (V), Mo (VI), W (IV), W (V), W (VI), Pd (ll), Ru (ll), Ru (lll), and Ru (IV). Preferred transition metals in the present transition metal bleach catalyst include manganese iron and chromium. More generally, the MRLs (and the corresponding transition metal catalysts) suitably comprise the present: (a) at least one major macrocycle ring comprising 4 or more heteroatoms; and (b) a covalently connected non-metallic superstructure capable of increasing the rigidity of the selected macrocycle preferably between: (i) a bridging superstructure, such as a link portion; (ii) a cross-bridging superstructure, such as a cross-bridging link portion; and (iii) combinations thereof. The term "superstructure" is used herein as defined in the literature Busch et al .; see, for example, Busch's articles in "Chemical Reviews". The preferred superstructures of the present not only enhance the stiffness of the macrocycle of origin, but also favor the bending of the macrocycle so that it coordinates to a metal in a slit. Suitable superstructures can be remarkably simple, for example, a linker portion can be used, such as any of those illustrated in formula 1 and formula 2 below: (CH2) n Formula 1 in which n is an integer, for example 2 to 8, preferably less than 6, typically 2 to 4, or Formula 2 in which m and n are integers of about 1 about 8, more preferably 1 to 3; Z is N or CH; and T is a compatible substituent, for example H, alkyl, trialkylammonium, halogen, nitro, sulfonate or the like. The aromatic ring in formula 2 can be replaced by a saturated ring, in which the atom in Z which is connected to the ring can contain N, O, S or C. Suitable MRLs are further illustrated in a non-limiting manner by the following compound : Formula 3 This is an MRL according to the invention which is highly preferred, cross stippling, methyl substituted derivative (all nitrogen atoms tertiary) of cyclamate. Formally, this ligand is called 5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane using the extended von Baeyer system. See "A Guide to IUPAC Nomenclature of Organic Compounds: Recommendations 1993", R. Pánico, W. H. Powell and J-C Richer (Eds.), Blackwell Scientific Publications, Boston, 1993; see especially section R-2.4.2.1. The macrocyclic rigid ligand transition metal bleach catalysts which are suitable for use in the compositions of the invention may generally include known compounds in which they conform to the definition herein, as well as, more preferably any of a large number of novel compounds expressly designated for the present uses in laundry, and illustrated in a non-limiting manner by any of the following: Dichloro-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2.] hexadecane- manganese (II) Diacuo-5,12-dimethyl-1, 5,8,12-tetraazabicyclo- [6,6.2.] hexadecane-manganese (II) Hexafluorophosphate, aqueous-hydroxy-5,12-dimethyl-1 hexafluorophosphate 5,8,12-tetraaza-blciclo [6.6.2.] Hexadecane-manganese (lll) Diacuo-5,12-dimethyl-1, 5,8,12-tetraazabicyclo- [6.6.2.] Hexadecane-manganese tetrafluoroborate (II) Dichloro-5,12-dimethyl-1, 5,8,12-tetraazabicyclo- [6,6.2.] Hexadecane-manganese (III) dichloro-5,12-di-nb hexafluorophosphate util-1, 5,8,12-tetraazabicyclo [6.6.2.] hexa-decane-manganese (II) Dichloro-5,12-dibenzyl-1, 5,8,12-tetraazabicyclo [6.6.2.] hexadecane- manganese (II) Dichloro-5-n-butyl-12-methyl-1, 5,8,12-tetraaza-bicicon [6.6.2.] hexa-decane-manganese (II) Dicioro-5-n-octyl-12 -methi-1, 5,8,12-tetraaza-bicyclo [6.6.2.] hexa-decane-manganese (II) Dichloro-5-n-butyl-12-dimethyl-1, 5,8,12-tetraaza- bicyclo [6.6.2.] hexa-decane-manganese (II). As a practical matter and not by way of limitation, the laundry compositions and methods herein can be adjusted to provide in order at least one part per one hundred million active species of bleach catalyst in the washing medium. aqueous and will preferably provide approximately 0.01 ppm ppm, more preferably from about 0.05 ppm to about 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm, of the wash solution bleach catalyst species. In order to obtain such levels in the washing solution of an automatic washing process, typical compositions herein will comprise from about 0.0005% about 0.2%, more preferably from about 0.004% to about 0. 08%, of bleaching catalyst, especially manganese or cobalt catalysts, by weight of the bleaching compositions. d) Other Bleach Catalysts The compositions herein may comprise one or more additional bleach catalysts. Preferred bleach catalysts are zwitterionic bleach catalysts, which are described in the U.S.A. No. 5,576,282 (especially 3- (3,4-dihydroisoquinolinio) propane sulfonate Other bleach catalysts include cationic bleach catalysts as described in U.S. Patent Nos. 5,360,569, 5,442,066, 5,478,357, 5,370,826, 5,482,515, 5,550, 256 , and WO 95/13351, WO 95/13352 and WO 95/13353.Preformed peracids, such as pftalimido-peroxycaproic acid ("PAP") are also suitable as bleaching agents. See, for example, US Pat. 5,487,818, 5,310,934, 5,246,620, 5,279,757 and 5,132,431.

Enzyme Stabilizers Enzymes can be stabilized for use in detergents by various techniques. Enzyme stabilization techniques are set forth and exemplified in the patents of E.U.A. 3,600,319, EP 199,405 and EP 200,586. Enzyme stabilization systems are also described, for example, in the U.S. patent. at 3,519,570. A useful bacillus, AC13 species that gives proteases, silanases and cellulases, is described in patent WO 9401532. The enzymes employed herein can be stabilized by the presence of water soluble sources of calcium and / or magnesium ions in the compositions which provide such ions to the enzymes. Suitable enzyme stabilizers and levels of use are described in US Patents Nos. 5,705,464, 5,710,115 and 5,576,282.

Detergency Meters The detergent and laundry compositions described herein preferably comprise one or more builders or builders. When present, the compositions will typically comprise at least about 1% builder, preferably about 5%, more preferably from about 10% to about 80%, preferably about 50%, more preferably about 30% by weight , of detergency improver. Do not mean to say that lower or higher levels of detergency builder are excluded, however. Preferred detergency builders for use in detergent and laundry compositions, particularly dishwashing compositions, described herein include, but are not limited to, water-soluble builder compounds (e.g. polycarboxylates), as is described in the US patent Nos. 5,695,679, 5,7058,464 and 5,710,115. Other suitable polycarboxylates are exposed, in the patents of E.U.A. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly the titrates. Inorganic or P-containing builders include, but are not limited to, alkali metal, ammonium and alkanol ammonium salts of polyphosphates (exemplified by tripolyphosphates, pyrophosphates, and vitreous polymeric meta-phosphates), phosphonates (see, for example, for example, U.S. Patent Nos. 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137), phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminum silicates. However, detergency builders other than phosphate are required in some places. Importantly, the compositions herein work surprisingly well even in the presence of so-called "weak" builders (as compared to phosphates), such as citrate, or the so-called "poorly improved detergency" situation that can occur with the detergents of zeolite or stained silicate. Suitable silicates include water-soluble sodium silicates with a SiO: NaO ratio of about 1.0 to 2.8., preferred in the ratios of about 1.6 to 2.4 and the ratio of about 2.0 being most preferred. The silicates can be formed either of the anhydrous salt or of a hydrated salt. Sodium silicate with a Si02: Na20 ratio of 2.0 is most preferred. The silicates, when present, are preferably present in the detergent and laundry compositions described herein at a level of from about 5% to about 50% by weight of the composition, more preferably from about 10% to about 40% by weight . The partially soluble or insoluble builder compounds, which are suitable for use in detergent or laundry compositions, particularly in granular detergent compositions, include, but are not limited to, crystalline layered silicates, preferably layered sodium silicates. crystalline (partially water soluble), as described in the US patent No. 4,664,839, and sodium aluminosilicates (insoluble in water). When present in the detergent and laundry compositions, these builders are typically present at a level of from about 1% to 80% by weight, preferably and about 10% to 70% by weight, most preferably and about 20% to 60% by weight. % by weight of the composition. The crystallized statified sodium silicates having the general formula NaMSi? O ^ + 1 and H20 in which M is sodium or hydrogen, x is a number from about 1.9 to about 4, preferably and about 2 to about 4, most preferably 2, ey is a number of about 0 about 20, preferably 0, the compositions described herein can be used. Crystallized layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043. The most preferred material is delta-Na2S0, obtainable from Hoechst AG as NaSKS-6 (commonly abbreviated herein as "SKS-6"). Unlike the zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. The Na SKS-6 has the shape of stratified silicate delta-Na2SiOs morphology. SKS-6 is a highly preferred layered silicate for use in the compositions described herein, but other layered silicate metals, such as those having the general formula NaMsi? 02X + 1 and H20 in which M is sodium or hydrogen, x is a number of 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0, in the compositions described herein. Others ranging in Hoechst stratified silicates include NaSKS-5, Na SKS-7 and Na SKS-1 1, as alpha, beta and gamma forms. As indicated above, delta-Na2Si5 (NaSKS-6 asmo) is very preferred for use herein. Other silicates may also be useful, such as for example magnesium silicate, which could serve as a curling agent in granular formulations, as a stabilizing agent for oxygen bleach and as a component of foam control systems. The crystallized statified sodium silicate material is preferably present in granular detergent compositions as a particulate material intimately mixed with a water soluble solid ionizable material. The water-soluble solid ionizable material is preferably selected from among organic acids, salts of organic and inorganic acids, and mixtures thereof. Aluminosilicate builders are of great importance in the majority of commonly used strong working granular detergent compositions, and can be a significant detergency enhancing ingredient in liquid detergent formulations. The aluminosilicate detergency builders have the empirical formula: where z and y are integers at least equal to 6, the molar ratio of zay is in the range of 1.0 to about 0.5, and x is an integer of about 15 to 264. Preferably, the aluminosilicate builder is an aluminosilicate zeoiite having the unit cell formula: Na [(AI02 ) z (Si? 2) and] -xH20 in which z and y are at least equal to 6; the molar ratio of zay is from 1.0 to 0.5 and x is at least 5, preferably 7.5 to 276, more preferably from 10 to 264. The aluminosilicate builders are preferably in hydrated form and are preferably crystalline, containing about 10% to about 28%, more preferably from about 18% to about 22% water in bound form.

These aluminosilicate ion exchange materials may be of crystalline or amorphous structure and may be aluminosilicates present in nature or synthetically derived. A method for producing aluminosilicate ion exchange materials is set forth in the U.S.A. 3,985,669. The preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are obtainable with the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite MAP and Zeolite HS and mixtures thereof. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: Na12 [(AI02) 12 (SiO2) 12] -xH20 wherein x is from about 20 to about 30, especially about 27. It is known this material as Zeolite A. Dehydrated zeolites (x = 0-10) can also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter. Zeolite X has the formula: Na86 [(AIO2) 86 (SiO2) 106] -276H2O Citrate builders, for example citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders. Particular importance for liquid detergent formulations of strong work, due to its availability of renewable sources and its biodegradability. Citrates can also be used in the granular compositions, especially in combination with zeolite builders and / or layered silicate. Oxydisuccinates are also especially useful in such compositions and combinations. Also suitable in the detergent compositions described herein are 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds set forth in U.S. Pat. 4,566,984. Useful succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids, and salts thereof. A particularly preferred compound of that type is dodecenylsuccinic acid. Specific examples of succinate builders include: lauryl succinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Lauryl succinates are the preferred builders of this group and are described in European patent application 86200690.5 / 0,200,263 published on November 5, 1986. Fatty acids, for example, C12-C18 monocarboxylic acids, can also be incorporated by themselves. the composition, or in combination with the aforementioned detergency builders, especially citrate and / or succinate builders, to provide additional builder activity. Such use of fatty acids will generally result in a decrease in foaming, which should be taken into account by the formulator.

Dispersants One or more suitable polyalkyleneamine dispersants may be incorporated into the laundry compositions of the present invention. Examples of suitable dispersants can be found in European Patent Applications Nos. 111, 965, 111, 984, and 112,592; the patents of E.U.A. Nos. 4,597,898, 4,548,744 and 5,565,145. However, any clay / dirt dispersing or anti-redeposition agent can be used in the laundry compositions of the present invention. In addition, polymeric dispersing agents including polymeric polycarboxylates and polyethylene glycols are suitable for use in the present invention. Unsaturated monomeric acids which can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from about 2., 000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers may include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. It has been disclosed in the use of polyacrylates of this type in detergent compositions, for example, in the U.S. patent. 3,308,067. Acrylic / maleic acid based polymers can be used as the 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 such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio of the acrylate segment to the maleate in such copolymers will generally vary from about 30: 1 to about 1: 1, more preferably from about 10: 1 to 2: 1. The water-soluble salts of such copolymers of acrylic acid and maleic acid may include, for example, alkali metal, ammonium and substituted ammonium salts. Soluble acrylate / maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982, as well as EP 193,360, published on September 3, 1986, which describes also such polymers comprising hydroxypropylacrylate. Other useful thickening agents still include the terpolymers of maleic acid, acrylic acid and vinyl alcohol. Such materials are also disclosed in EP 193,360, including, for example, the terpolymer at 45/45/10 of acrylic acid, maleic acid and vinyl alcohol.

Another polymeric material that can be included is polyethylene glycol (PEG). PEG can exhibit a dispersing agent function in addition to acting as a clay and dirt removing and anti-redeposition agent. Typical ranges of molecular weights for these purposes vary from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000. Dispersing agents of polyaspartate and polyglutamate can also be used especially in conjunction with the zeolite builders. Dispersing agents, such as polyaspartate, preferably have a molecular weight (on average) of about 10,000.

Dirt release agents The compositions according to the present invention may optionally comprise one or more soil release agents. If used, the soil release agents will generally comprise from about 0.01%, preferably from about 0.1%, more preferably from about 0.2% to about 10%, preferably to about 5%, more preferably to about 3% by weight, of the composition. Non-limiting examples of suitable soil release polymers are set forth in U.S. Patents. Nos. 5,728,671; 5,691, 298; 5,599,782; 5,415,807; 5,182,043; 4,956,447; 4,976,879; 4,968,451; 4,925,577; 4,861, 512; 4,877,896; 4,771, 730; 4,711, 730; 4,721, 580; 4,000,093; 3,959,230; and 3,893,929; and European patent application 0 219 048. Other suitable soil release agents are described in the U.S. Patents. Nos. 4,201, 824, 4,240,918, 4,525,524, 4,579,681, 4,220,918 and 4,787,989; EP 279,134 A; EP 457,205A and DE 2,335,044.

Chelating Agents The compositions of the present invention may also optionally contain a chelating agent which serves to chelate metal ions and metal impurities which would otherwise tend to deactivate bleaching agents. Useful chelating agents can include aminocarboxylates, phosphonates, aminophosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof. Other examples of suitable chelating agents and levels of use are described in the U.S. Patents. Nos. 5,705,464, 5,710,115, 5,728,671 and 5,576,282. The compositions herein may also contain salts of water-soluble glycolindiacetic acid (MGDA) (or acid form) as a chelating agent or as a builder, useful for example with insoluble builders, such as zeolites, layered silicates and the like. .

If used, these chelating agents will generally comprise from about 0.1% to about 15%, more preferably from about 0.1% to about 3.0% by weight of the detergent compositions herein.

Foam suppressor Another optional ingredient is a foam suppressor, exemplified by silicones and silica-silicone blends. Examples of suitable foam suppressors are set forth in the U.S. Patents. Nos. 5,707,950 and 5,728,671. These foam suppressors are normally employed at levels from 0.001% to 2% by weight of the composition, preferably from 0.01% to 1% by weight.

SOFTENING AGENTS Fabric softening agents can also be incorporated into the laundry detergent compositions according to the present invention. The inorganic softening agents are exemplified by the smectite clays exposed to the patents GB-A-1 400 898 and U.S. 5,019,292. Organic softening agents include water-insoluble tertiary amines as set forth in GB-A-1 514 276 and EP-B-011 340 and their combination with C12-C14 monoquaternary ammonium salts is disclosed in EP documents. -B-026 527 and EP-B-026 528 and dilarga chain amides are disclosed in EP-B-0 242 919. Other useful organic ingredients of fabric softening systems include high-weight polyethylene oxide materials molecular structure as disclosed in EP-A-0 299 575 and 0 313 146. Particularly suitable fabric softening agents are exposed, in the patents of E.U.A. Nos. 5,707,950 and 5,728,673. Smectite clay levels are usually in the range of 2% to 20%, more preferably 5% to 15% by weight, the material being added as a dry mixed component to the remainder of the formulation. Organic fabric softening agents, such as water insoluble tertiary amines or dilarga chain amine materials, are incorporated at levels of 0.5% to 5% by weight, usually from 1% to 3% by weight, while the materials are added. of high molecular weight polyethylene oxide and water-soluble cationic materials, at levels of 0.1% to 2%, usually from 0.15% to 1.5% by weight. These materials are normally added to the spray-dried portion of the composition, although in some cases it may be more convenient to add them as a dry mixed particulate material or sprinkle them as molten liquid over other solid components of the composition. The biodegradable quaternary ammonium compounds described in EP-A-040 562 and EP-A-239 910 have been presented as alternatives to the traditionally used dilarga alkyl chain ammonium chlorides and methylsulfates.

Non-limiting examples of anions compatible with softeners for the quaternary ammonium compounds and amine precursors include chloride or methylisulfate.

Inhibition of dye transfer The detergent compositions of the present invention may also include compounds for inhibiting the transfer of dye from one fabric to another of solubilized or suspended dyes that are encountered during fabric washing and conditioning overlays involving fabrics of color.

Polymeric dye transfer inhibiting agents The detergent compositions according to the present invention can also comprise from 0.001% to 10%, preferably from 0.01% to 2%, more preferably from 0.05% to 1% by weight of transfer inhibiting agents of polymeric dyes. Said polymeric dye transfer inhibiting agents are normally incorporated into the detergent compositions in order to inhibit the transfer of dyes from the colored fabrics to the fabrics washed therewith. These polymers have the ability to complex or absorb fugitive dyes extracted by washing the colored fabrics before the dyes adhere to other articles in the wash.

Especially suitable polymeric dye transfer inhibiting agents are polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polymers of polyvinylpyrrolidone, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. Examples of such dye transfer inhibiting agents are set forth in the U.S. Patents. Nos. 5,707,950 and 5,707,951. Additional suitable dye transfer inhibiting agents include, but are not limited to, entangled polymers. The entangled polymers are polymers whose base structure is interconnected to a certain degree; these links can be of a physical or chemical nature, possibly with active groups n on the base structure and on the ramifications; crosslinked polymers have been described in the Journal of Polymer Science, volume 22, pages 1035-1039. In one embodiment, the entangled polymers are made in such a way that they form a rigid three-dimensional structure, which can trap dyes in the pores formed by the three-dimensional structure. In another embodiment, the entangled polymers trap the dyes by swelling. Such entangled polymers are described in co-pending European patent application 94870213.9. The addition of such polymers also enhances the performance of the enzymes according to the invention. pH and variation of pH regulation Many of the laundry detergent compositions described herein are adjusted in their pH, ie they are relatively resistant to pH decrease in the presence of acid soils. However, other compositions herein may have exceptionally low pH regulation capacity or may be substantially unregulated in their pH. Techniques for controlling or varying the pH to recommended levels of use more generally include the use not only of pH regulators, but also additional alkalis, acids, pH leap systems, double compartment vessels, etc., and are well known for those skilled in the art.

Other materials The detersive ingredients or adjuncts optionally included in the present compositions may include one or more materials to aid or enhance laundry performance, the treatment of the substrate to be cleaned or designed to improve the static of the compositions. Attachments that may also be included in the compositions of the present invention, at their levels established in the conventional art for use (generally, the adjunct materials comprise, in total, from about 30% to about 99.9%, preferably about 70 % to approximately 95%, by weight of the compositions) include other active ingredients, such as phosphate-free builders, color mounts, plant care, anti-rust and / or anti-corrosion agents, colorants, fillers, germicides, alkalinity sources, hydrotropes, antioxidants, perfumes, solubilizing agents, carriers, processing aids, pigments and pH control agents, as described in the US patents Nos. 5,705,464, 5,710,115, 5,698,504, 5,695,679, 5,686,014 and 5,646,101.

Laundry Methods In addition to the methods for laundry fabrics described herein, the invention also includes herein a laundry pretreatment process for fabrics that have been soiled or stained, comprising directly contacting said stains and / or soils. with a highly concentrated form of the laundry composition set forth above before washing such fabrics, using conventional aqueous wash solutions. Preferably, the laundry composition remains in contact with the soil / stain for a period of about 30 seconds to 24 hours before washing the pretreated / conventional soiled / stained substrate. More preferably, the types of pretreatment will vary from about 1 to 180 minutes.

Product with instructions for use The present invention also covers the inclusion of instructions on the use of the compositions containing enzyme granules of the present invention with the packages containing the compositions herein or with other forms of advertising associated with the sale and the use of the compositions. The instructions may be included in any manner typically used by consumer product manufacturing or supply companies. Examples include providing instructions on a label attached to the container containing the composition; on a sheet either attached to the container or accompanying it when it is purchased; or of announcements, demonstrations and / or other written or oral instructions that may be related to the purchase or use of the compositions. Specifically, the instructions will include a description of the use of the composition, for example, the recommended amount of the composition to be used in a washing machine to clean the fabric; the recommended amount of the composition to be applied to the fabric; if soaking or carving is appropriate. The compositions of the present invention are preferably included in a product. The product preferably comprises a composition comprising one or more enzyme granules of the present invention and optionally one or more cleaning adjunct materials, and further comprising instructions for using the product in the washing of fabrics, contacting a fabric in need of cleaning with an effective amount of the composition, such that the composition cleans the fabric. Although particular embodiments of the present invention have been described, it will be obvious to those skilled in the art that various changes and modifications of the present invention can be made, without departing from the spirit and scope of the invention. It is intended to cover, in the appended claims, all such modifications that are within the scope of the invention. The compositions of the present invention can be suitably prepared by any method chosen by the formulator, examples of which are described in US Patents. 5,691, 297, Nassano et al., Issued November 11, 1997; patent of E.U.A. 5,574,005, Welch et al., Issued November 12, 1996; patent of E.U.A. 5,569,645, Dinniwell et al., Issued October 29, 1996; patent of E.U.A. 5,565,422, Del Greco et al., Issued October 15, 1996; patent of E.U.A. 5,516,448, Capeci et al., Issued May 14, 1996; patent of E.U.A. 5,489,392, Capeci et al., Issued February 6, 1996; patent of E.U.A. 5,486, 303, Capeci et al., Issued January 23, 1996, all of which are incorporated herein by reference. In addition to the above examples, the compositions of the present invention can be formulated as any suitable laundry detergent composition, non-limiting examples of which are described in US Patents. 5,679,630, Baeck et al., Issued October 21, 1997; patent of E.U.A. 5,565,145, Watson et al., Issued October 15, 1996; patent of E.U.A. 5,478,789, Fredj et al., Issued December 26, 1995; U.S. Patent 5,470,507, Fredj et al., issued November 28, 1995; patent of E.U.A. 5,466,802, Panadiker et al., Issued November 14, 1995; U.S. Patent 5,460,752, Fredj et al., issued October 24, 1995; U.S. Patent No. 5,458,810, Fredj et al., issued October 17, 1995; U.S. Patent: A: 5,458,809, Fredj et al., issued October 17, 1995; U.S. Patent: A: 5,288,431, huber et al., issued February 22, 1994, all of which are incorporated herein by reference. Having described the invention in detail with reference to the preferred embodiments and examples, it will be apparent to those skilled in the art that various changes and modifications may be made without departing from the scope of the invention and the invention is not considered to be limited to what is describes in the specification.

Claims (11)

NOVELTY OF THE INVENTION CLAIMS

1. - An enzyme granulate comprising: (a) one or more enzyme granule density reducing components; and (b) one or more enzymes.

2.- The enzyme granulate in accordance with the claim 1, further characterized in that one or more enzyme granule density reducing components are selected from the group consisting of microspheres, cavity forming components, pore forming components and mixtures thereof, preferably microspheres, more preferably because said microspheres are made of one or more materials selected from the group consisting of plastics, proteins, siliceous materials, ceramics and mixtures thereof.

3.- The enzyme granulate in accordance with the claim 2, further characterized in that said microspheres are made of one or more plastics selected from the group consisting of thermoplastics, acylonitrile, methacrylonitrile, polyacrylonitrile, polymethacrylonitrile and mixtures thereof.

4. The enzyme granulate according to claim 2, further characterized in that said microspheres are made of one or more siliceous materials selected from the group consisting of glass.

5. - The enzyme granulate according to any of the preceding claims, further characterized in that said microsphere is capable of expanding with a means for expanding, preferably selected from the group consisting of liquid hydrocarbons, gases and mixtures thereof contained within said microspheres , in such a way that it increases the volume of the microsphere.

6. The enzyme granulate according to any of claims 2-5, further characterized in that said microsphere is made of a material, such that the density of the expanded microsphere is less than 0.4 g / ml, preferably less than 0.2 g / ml, more preferably less than 0.1 g / ml.

7. A laundry detergent composition comprising an enzyme granulate according to any of the preceding claims and one or more laundry adjunct materials.

8. The detergent composition for laundry according to claim 7, further characterized in that the laundry detergent composition and the enzyme granulate have densities, such that the density difference between the density of said laundry detergent composition and the The density of said enzyme granulate is less than 0.2 g / ml, preferably less than 0.1 g / ml, more preferably less than 0.05 g / ml.

9. The detergent composition for laundry according to claim 7 or 8, further characterized in that the laundry detergent composition is in a form selected from the group consisting of non-aqueous liquid laundry detergent compositions, aqueous liquid laundry detergent compositions, detergent compositions for laundry gel, granular laundry detergent compositions or powder laundry detergent compositions.

10. A product comprising the detergent composition for laundry according to any of claims 7-9, further characterized in that the product also comprises instructions for using said product to wash fabrics in need of cleaning, contacting said fabrics with a effective amount of said product, such that the composition cleans said fabrics.

11. The use of the laundry detergent composition as claimed in any of claims 7-9 for washing fabrics.