MXPA00000834A - Detergent compositions containing mixtures of crystallinity-disrupted surfactants - Google Patents

Abstract

A cleaning composition comprising:a) about 0.1%to about 99.9%by weight of said composition of an alkylarylsulfonate surfactant system comprising from about 10%to about 100%by weight of said surfactant system of two or more crystallinity-disrupted alkylarylsulfonate surfactants of the formula:(B-Ar-D)a(Mq+)b (defined herein after);and b) from about 0.00001%to about 99.9%by weight of said composition of cleaning composition adjunct ingredients, at least one of which is selected from the group consisting of:i) detersive enzymes;ii) organic detergent builders;iii) oxygen bleaching agent;iv) bleach activators;v) transition metal bleach catalysts;vi) oxygen transfer agents and precursors;vii) polymeric soil release agents;viii) water-soluble ethoxylated amines having clay soil removal and antiredeposition properties;ix) polymeric dispersing agents;x) polymeric dye transfer inhibiting agents;xi) alkoxylated polycarboxylates;and xii) mixtures thereof.

Description

old DETERGENT COMPOSITIONS CONTAINING MIXTURES OF TENSIOACTIVE AGENTS ALTERED IN THEIR CRYSTAL1NITY FIELD OF THE INVENTION The present invention relates to cleaning compositions comprising an alkylarylsulfonate surfactant system containing a mixture of isomers of interrupted crystallinity, preferably branched alkylarylsulfonate surfactants and optionally one or more surfactant alkylarylsulfonates without interrupted crystallinity. The cleaning compositions also contain a detergent builder which is selected from detersive enzymes, detergents, organic detergents, oxygen bleaching agent, bleach activators, transition metal bleach catalysts, oxygen transfer agents and precursors, polymeric agents soil releasers, water-soluble ethoxylated amines having clay grime removal and anti-redeposition properties, polymeric dispersing agents, polymeric dye transfer inhibiting agents, alkoxylated polycarboxylates and mixtures thereof. The cleaning composition also typically contains additional detergency ingredients of the cleaning composition. These cleaning compositions are especially useful in detergent compositions which will be used in laundry processes involving hard water or low temperature water washing conditions. BACKGROUND OF THE INVENTION Historically, highly branched alkylbenzene sulfonate surfactants, such as those based on tetrapropylene (known as "ABS") are used in detergents. However, it is found that these are poorly biodegradable. This was followed by a prolonged period of improvement of manufacturing processes by alkylbenzene sulfonates, making them as straight as possible ("LAS"). The overwhelming part of a large amount of the preparation of the straight alkylbenzene sulfonate surfactant is directed towards this objective. All relevant large-scale commercial alkylbenzene sulfonate processes in current use are directed to straight alkylbenzene sulphonates. However, straight alkylbenzene sulphonates are not without limitations; for example, it would be more desirable if they exhibited improved properties for hard water and / or cleaning properties in cwater. Therefore, they often do not produce good cleaning results, for example when formulated with different phosphate builders and / or when used in hard water areas. As a result of the limitations of alkylbenzene sulfonates, consumer cleaning formulations often need to include a high level of cosurfactants, builders, and other builders that have been necessary to give a higher alkylbenzene sulfonate.

Accordingly, it would be very desirable to simplify detergent formulations and provide better performance and better value to the consumer. Furthermore, in view of the very large tonnages of alkylbenzenesulfonate surfactants and detergent formulations used throughout the world, even modest improvements in the performance of a basic alkylbenzene sulfonate detergent can generate a large result. In order to understand the technique of elaboration and use of sulfonated alkylaromatic detergents it should be appreciated that it is advanced through many stages and that they include: (a) the early manufacture of non-biodegradable highly branched LAS (ABS); (b) the development of processes such as processes catalyzed by ATF or AICI3 (note that each process provides a different composition, for example HF / olefin provides 2-lower phenyl of the AICI3 / classic chloroparaffin typically giving byproducts which although perhaps useful due to solubility, they are undesirable due to biodegradation); (c) the market changes to LAS in which a large proportion of the alkyl is straight; (d) improvements that include what are called "2-phenyl high" or DETAL processes (in fact it is not really 2-phenyl "high" due to solubility problems when the hydrophobe is too straight); and (e) recent improvements in the compression of biodegradation. The alkylbenzene sulfonate detergent technique is replete extraordinarily with references which describe for and against each aspect of these compositions. For example, part of the art describes high 2-phenyl as desirable, while another technique describes exactly in the opposite direction. In addition, there are many erroneous teachings and technical misconceptions about the operating mechanism of LAS under conditions of use, particularly in the area of hardness tolerance. The large volume of such references bases the technique in its entirety and make it difficult to select the useful teachings from the useless ones without large amounts of repeated experimentation. To further understand the state of the art, it should be appreciated that there has been not only a lack of clarity on how to correct the unresolved problems of linear LAS, but also a large number of misconceptions, not only in understanding of biodegradation but also in the basic mechanisms of LAS operation in the presence of hardness. According to the literature, and general practice surfactants having alkaline or alkaline earth salts that are relatively insoluble (their Na or Ca salts have a relatively high Kraft temperature) are less desirable than those having alkali or alkaline earth salts which have a relatively higher solubility (Na or Ca salts having lower Kraft temperature). In the literature, mixtures of LAS in the presence of Ca or Mg hardness are said to precipitate. It is also known that the 2- or 3-phenyl or "terminal" isomers of LAS have higher Kraft temperatures than, for example, the 5- or 6-internal "phenyl" isomers. Therefore, it would be expected that changing a LAS composition to increase the content of 2- and 3-phenyl isomer could decrease tolerance to hardness and solubility; which is not a good idea. On the other hand, it is also known that the construction conditions under which both the internal phenyl isomers 2- and 3-phenyl of equal chain length can be soluble, the 2- and 3-phenyl isomers are more surface-active materials. Therefore, it would be expected that changing a LAS composition to increase the content of 2- and 3-phenyl isomer could increase cleaning performance. However, unresolved problems remain regarding solubility, hardness, tolerance and low temperature operation.

ANTECEDENTS OF THE TECHNIQUE The documents US 5,026,933; US 4,990,718; US 4,301, 316; US 4,301, 317; US 4,855,527; US 4,870,038; US 2,477,382; EP 466,558, 1/15/92; EP 469,940, 2/5/92; FR 2,697,246, 4/29/94; US 793,972, 1/7/81; US 2,564,072; US 3,196,174; US 3,238,249; US 3,355,484; US 3,442,964; US 3,492,364; US 4,959,491; WO 88/07030, 9/25/90; US 4,962,256, US 5,196,624; US 5,196,625; EP 364,012 B, 2/15/90; US 3,312,745; US 3,341, 614; US 3,442,965; US 3,674,885; US 4,447,664; US 4,533,651; US 4,587,374; US 4,996,386; US ,210,060; US 5,510,306; WO 95/17961, 7/6/95; WO 95/18084; US 5,510,306; US 5,087,788; 4,301, 316; 4,301, 317, 4,855,527; 4,870,038; 5,026,933; 5,625,105 and 4,973,788 are useful as background for the invention. The manufacture of alkylbenzenesulfonate surfactants has been recently reviewed. See volume 56 in the series "Surfactant Science" Marcel Dekker, New York, 1996, which includes in particular Chapter 2 entitled "Alkylarylsulfonates: History, Manufacture, Analysis and Environmental Properties", pages 39-108 which includes 297 literature references. The documents referred to herein are incorporated in their entirety.

BRIEF DESCRIPTION OF THE INVENTION It has now surprisingly been found that when an alkylarylsulfonate surfactant system includes two or more isomers of alkylarylsulfonate surfactants of interrupted crystallinity, which optionally also contain one or more alkylarylsulfonate surfactants without interrupted crystallinity, there is a surprising increase in performance over the surfactant system of alkylarylsulfonate which does not include the isomers of alkylarylsulfonate surfactant of interrupted crystallinity. The present invention has numerous advantages that surpass one or more of the aspects identified in the foregoing, which include but are not limited to: superior solubility in cold water, for example laundry in cold water; superior tolerance to hardness; and excellent detergency. In addition, the invention is expected to provide a reduced accumulation of old fabric softener residues from fabrics which are subjected to laundry process and an improved removal of lipid or fat residues from the fabrics. Benefits are also expected in non-laundry cleaning applications, such as dish cleaning. The development offers substantial improvements expected in the manufacturing facility of relatively high 2-phenylsulfonate compositions, improvements also in the ease of processing and quality of the resulting detergent formulations and attractive economic advantages. The present invention is based on the unexpected discovery that there exist, in the middle range between the highly branched and old non-biodegradable alkylbenzenesulfonate, and the new straight types, certain alkylbenzene sulfonates which function much better than the latter and are more biodegradable than the previous ones. The new alkylbenzene sulfonates are easily accessible by several of the many known alkylbenzene sulfonate processes. For example, the use of certain dealuminated mordenites allows convenient manufacturing. In accordance with the present invention, a novel cleaning composition is provided. This novel cleaning composition comprises: a) about 0.1% to about 99.9% by weight of the composition of an alkylarylsulfonate surfactant system comprising from about 10% to about 100% by weight of the surfactant system of two or more alkylarylsulfonate surfactants of crystallinity interrupted of formula (B-Ar-D) to (Mq +) b where D is SO3-, M is a cation or a mixture of cations, q is the valence of the cation, a and b are the numbers that are selected so that the composition is electroneutra; Ar is selected from benzene, toluene and combinations thereof; and B comprises the sum of at least one primary hydrocarbyl portion containing from 5 to 20 carbon atoms, preferably 7 to 16, more preferably 9-15, much more preferably 10-14 carbon atoms and one or more carbon atoms. more portions of interrupted crystallinity wherein portions of interrupted crystallinity interrupt or branch off the hydrocarbyl portion; and wherein the alkylarylsulfonate surfactant system has an interruption in crystallinity to the extent that its critical sodium solubility temperature as measured by the CST test is no greater than about 40 ° C, and wherein the surfactant alkylarylsulfonate system has at least one of the following properties: the percentage of biodegradation, as measured by the modified SCAS test, exceeds that of tetrapropylenebenzene sulfonate; and the weight ratio of non-quaternary carbon atoms to quaternary atoms in B is at least about 5: 1 (preferably at least about 10: 1, more preferably at least about 100: 1); and b) from about 0.00001% to about 9.9% by weight of the composition of the builder ingredients of the cleaning composition, at least one of which is selected from the group consisting of: i) detersive enzymes, which are preferably selected of proteases, amylases, lipases, cellulases, peroxidases and mixtures thereof; ii) organic detergent builders, which are preferably selected from polycarboxylate compounds, hydroxypolycarboxylate ether, substituted ammonium salts of polyacetic acids and mixtures thereof; iii) an oxygen bleaching agent, which is preferably selected from hydrogen peroxide, but inorganic hydrates, peroxo organic hydrates and organic peroxyacids, including hydrophilic and hydrophobic mono- and di-peroxyacids, and mixtures thereof; V) bleach activators, which are preferably selected from TAED, NOBS and mixtures thereof; v) transition metal bleach catalysts, preferably bleach catalysts containing manganese; vi) oxygen transfer agents and precursors; vii) polymeric soil release agents; viii) water-soluble ethoxylated amines that have clay grime removal and anti-redeposition properties; ix) polymeric dispersing agents; x) polymeric dye transfer inhibiting agents; xi) alkoxylated polycarboxylates; and xii) mixtures thereof. The cleaning composition will preferably contain at least about 0.1%, more preferably at least about 5%, even more preferably, still at least about 1% by weight of the composition of the surfactant system. The cleaning composition will also preferably contain at most about 80%, more preferably at most about 60%, even more preferably at most about 40% by weight of the composition of the surfactant system. The surfactant system will preferably contain at least about 15%, more preferably at least about 30%, even more preferably, still at least about 40% by weight of the surfactant system of two or more crystalline alkylarylsulfonate surfactants interrupted The surfactant system will preferably also contain at most about 100%, more preferably at most about 90%, even more preferably at most about 80% by weight of the surfactant system of two or more alkylarylsulfonate surfactants of interrupted crystallinity. Accordingly, it is an aspect of the present invention to provide novel cleaning compositions; these and other aspects, features and advantages will be apparent from the following detailed description and the appended claims. All percentages, ratios and proportions herein are by weight of the ingredients used to prepare the finished compositions, unless otherwise specified. All temperatures are in degrees Celsius (° C) unless otherwise specified. All documents mentioned herein are incorporated, in the pertinent part, as a reference in this document.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel cleansing compositions. Component (a) contains from about 0.1% to about 99.9% by weight of the composition of an alkylarylsulfonate surfactant system comprising from about 10% to about 100% by weight of the surfactant system of two or more alkylarylsulfonate surfactants of interrupted crystallinity , of formula (B-Ar-D) a (Mq +) b where D is SO3-, M is a cation or a mixture of cations. Preferably, M is an alkali metal, an alkaline earth metal, ammonium, substituted ammonium or mixtures thereof, more preferably sodium, potassium, magnesium, calcium or mixtures thereof. The valence of the cation, q, preferably 1 or 2. The numbers are selected so that the composition is electroneutral, a and b preferably are 1 or 2 and 1, respectively. Ar is preferably selected from benzene, toluene and combinations thereof, and more preferably benzene. B comprises the sum of at least a primary hydrocarbyl portion containing from 5 to 20 carbon atoms and one or more portions of interrupted crystallinity wherein the interrupted crystallinity portions interrupt or branch out from the hydrocarbyl portion. Preferably, B includes an odd and even chain length of the hydrocarbyl portion. That is, it is preferred that B is not limited to being all odd or all even in terms of the chain length of the hydrocarbyl portion. The primary hydrocarbyl portion of B has from 5 to 20, preferably 7 to 16 carbon atoms. There may be one to three portions of interrupted crystallinity. The portions of interrupted crystallinity interrupt or branch out from the hydrocarbyl portion. When the interrupted crystallinity portions are branches or these are preferably C1-C3 alkyl, C1-C3 alkoxy, hydroxy and mixtures thereof, more preferably C1-C3 alkyl, more preferably C1 alkyl. -C2 and even more preferably methyl. When the crystallinity switching portions interrupt the hydrocarbyl portion, preferably they are ether, sulfone, silicone and mixtures thereof, most preferably ether. It is preferred that the alkylarylsulfonate surfactants of interrupted crystallinity include two or more homologs. The "homologs" may vary in the number of carbon atoms contained in B. The "isomers" which are described hereinafter in greater detail, especially include those compounds that have different binding positions of the portions that interrupt crystallinity to B. It is also preferred that the alkylarylsulfonate surfactants of interrupted crystallinity include at least two "isomers" which are selected from: i) ortho-, meta- and para-based isomers at the positions of attachment of the substituents to Ar, or when Ar is a substituted or unsubstituted benzene. This means that B can be ortho-, meta- and para- with respect to D, B can be ortho-, meta- and para- with respect to a substituent on Ar different from D, D can be ortho-, meta- and para- , with respect to a substituent on Ar different from B or any other possible alternative; ii) position isomers based on the binding positions of the portions of crystallinity interrupted to the primary hydrocarbyl portion of B; and iii) stereoisomers based on chiral carbon atoms in B. It is further preferred that the alkylarylsulfonate surfactants of interrupted crystallinity include at least two isomers of type ii), more preferably at least four isomers of type ii). Preferably, at least about 60% by weight surfactant system of the alkylated crystallinity interrupted crystalline surfactants are in the form of isomers wherein Ar binds to B at the first, second or third carbon atom in the primary hydrocarbyl portion thereof. , more preferably about 70% or more, much more preferably about 80% or more.

An optional component of the compositions of the present invention is from about 0% to about 85% by weight of the surfactant system, of one or more alkylarylsulfonate surfactants without interrupted crystallinity of formula (L-Ar-D) a (Mq +) b where D, M, q, a, b, Ar are as defined above. L is a straight primary hydrocarbyl portion containing from 5 to 20 carbon atoms. Preferably, L is a straight hydrocarbyl portion having from 7 to 16 carbon atoms. The alkylarylsulfonate surfactant system has an interruption in crystallinity to the extent that the temperature of critical sodium solubility, measured as the CST test, which is defined below, is no greater than about 40 ° C, preferably at most about 20 ° C. C, more preferably at most about 5 ° C. It is also preferable that the critical calcium solubility temperature, as measured by the CST test, be below about 80 ° C, preferably not more than about 40 ° C, more preferably not more than about 20 ° C. The alkylarylsulfonate surfactant system also has at least one of the following properties: a) the percentage of biodegradation, as measured by the modified SCAS test (described later in this document), exceeds that of the tetrapropylenebenzene sulfonate; b) a weight ratio of non-quaternary carbon atoms to quaternaries in B of at least about 5: 1. Preferably, the weight ratio of nonquaternary to quaternary carbon atoms in B is at least about 10: 1, more preferably at least about 20: 1, and more preferably at least about 100: 1. More preferably, the percentage of biodegradation in absolute terms is preferably at least about 60%, more preferably at least 70%, still more preferably at least 80% and much more preferably at least 90%, measured by the modified SCAS test. The cleaning compositions of the present invention comprise a component (b) which is from about 0.00001% to about 99.9% by weight of the composition of a cleaning builder material. These cleaning builder materials as well as other cleaning builder materials optionally useful herein are described in detail below.

INTERRUPTION OF CRYSTALLINITY The term "of interrupted crystallinity" as defined herein means that the surfactant referred to is one that contains a hydrophobic portion that is selected to result in a surfactant which is packaged less efficiently in a crystalline network compared to as does a reference surfactant in which the hydrophobe is a pure straight hydrocarbon chain of the formula CH 3 (CH 2) n having a length or ranges of chain lengths comparable to that of the surfactant described. The interruption of crystallinity in general, flows from any of several modifications of the surfactant at the molecular level. Remarkably, a linear hydrophobic, such as that is, CH3 (CH2) 11-, which itself "has no interrupted crystallinity" can be modified to form an interrupted crystallinity structure according to the invention by inserting various portions such as the ether, silicone or sulfone portions within of the chain, as for example in: Me or O More preferably, the interruption of crystallinity occurs in the present when one or more branches of B are added to the structure, for example as in: Note with respect to the surfactants herein that have the formulas (B-Ar-D) a- (Mq +) b, and (L-Ar-D) a (Mq +) b that B represents a hydrophobe of interrupted crystallinity while L indicates a hydrophobe of crystallinity without interruption. In addition, in alternative terms, hydrophobe B of interrupted crystallinity comprises a primary portion which consists of: (i) all components in B different from the portions that disrupt crystallinity; and (ii) the portions that interrupt crystallinity. In a preferred embodiment, B has: (i) a portion having from 7 to 16 carbon atoms, and (ii) a portion that interrupts the crystallinity that is selected from: (a) branches (or "side chains") attached to B which in general may vary, but which are preferably selected from C 1 -C 3 alkyl, hydroxy and mixtures thereof, more preferably C 1 -C 3 alkyl, more preferably C 1 -C 2 alkyl, even more preferable, methyl; (b) portions which interrupt the structure of B, which are selected from ether, sulfone and silicone; and (c) mixtures thereof. Other portions of interrupted crystallinity mentioned herein include olefin.

TENSOACTIVE SYSTEM OF ALKYLLARSULFONATE An essential component of the cleaning composition of the present invention is a surfactant alkylarylsulfonate system. The alkylarylsulfonate surfactant system comprises an essential component of interrupted crystallinity. The present invention relates to cleaning compositions comprising at least two or more such alkylarylsulfonate surfactants of interrupted crystallinity and optionally one or more alkylarylsulfonate surfactants without interrupted crystallinity. These two components are described as follows: (1) INTERRUPTED GLASS ALKYLARSULFONATE SURFACTANTS The cleaning compositions of the present invention comprise an alkylarylsulfonate surfactant system which contains at least two or more alkylarylsulfonate surfactants of interrupted crystallinity having the formula (B-Ar-D) a (Mq +) b where D, B, M, q, a, b, Ar are as defined in the above. interrupted crystallinity alkylarylsulfonate surfactants include: (a), (b), (c), (), (e), (f). (g) OH (h), (i) (m), (n) and (o).

The structures (a) to (o) are only illustrative of some possible alkylarylsulfonate surfactants of interrupted crystallinity and are not intended to limit the scope of the invention. It is also preferred that the alkylarylsulfonate surfactants of interrupted crystallinity include at least two isomers which are selected from: i) ortho-, meta- and para-based isomers at the positions of attachment of the substituents to Ar, when Ar is a substituted or unsubstituted benzene. This means that B can be ortho-, meta- and para- with respect to D, B can be ortho, meta- and para- with respect to a substituent on Ar different from D, D can be ortho-, meta- and para- respect to a substituent on Ar different from B, or any other possible alternative; ii) position isomers based on the binding positions of the portions that interrupt the crystallinity with respect to the primary hydrocarbyl portion of B; and iii) stereoisomers based on chiral carbon atoms in B.

An example of two types of isomers (i) are structures (a) and (c). The difference is that the methyl in (a) is linked in position 5, but in (c) the methyl is attached in position 7. An example of two isomers of type (i) are structures (I) and (n) ). The difference is that the sulfonate group in (I) is meta- relative to the hydrocarbyl portion, but in (n) the sulfonate is ortho-to the hydrocarbyl portion. An example of two isomers of type (ni) are structures (c) and (d). The difference is that these isomers are stereoisomers. The chiral carbon is on the seventh carbon atom in the hydrocarbyl portion. (2) ALKYLARSULFONATE TENSIONES WITHOUT INTERRUPTED CRYSTALLINATION Current inventive cleansing compositions may optionally comprise an alkylarylsulfonate surfactant system which may contain one or more alkylarylsulfonate surfactants without interrupted crystallinity having the formula (L-Ar-D) a (Mq +) b where D, M, L, q, a, b, Ar, are as defined in the above. Possible alkylarylsulfonate surfactants without interrupted crystallinity include standard straight alkylbenzene sulphonates such as those commercially available, for example, so-called straight 2-phenyl straight alkylbenzenesulfonates, better known as conventional DETAL or LAS available from Huntsman or Vista. These straight alkylarylsulphonates can be added to alkylated crystallinity interrupted surfactants to provide an alkylarylsulfonate surfactant system used in the cleaning composition of the present invention. Alternatively, the alkylarylsulfonate surfactants without interrupted crystallinity and the interrupted crystalline alkylarylisulfonate surfactants are produced in the same reaction, possibly due to the somerization either before, during or after the reaction. The ratio of alkylarylsulphonate without interrupted crystallinity to alkylarylsulphonate with interrupted crystallinity depends on the catalyst used. Whichever catalyst is used, the surfactant system must have a critical solubility temperature of sodium no greater than about 40 ° C and either a percentage of biodegradation, as measured by the modified SCAS test, exceeding that of tetrapropylbenzenesulfonate, preferably greater than 60%, more preferably greater than 80% or a weight ratio of non-quaternary carbon atoms to quaternaries in B of at least about 5: 1.

EXAMPLE 1 Interrupted crystallinity surfactant system prepared by means of straight olefin isomerized in its main structure Step (a): At least partial reduction of the linearity of an olefin (by isomerization in its main structure of the preformed olefin with respect to the appropriate chain lengths for detergency of cleaning product) A mixture of 1 -decene, 1-undecene, 1 -dodecene and 1-tridecene (for example available from Chevron) in a weight ratio of 1: 2: 2: 1 is passed over a Pt-SAPO catalyst at 220 ° C and any suitable LHSV, for example 1.0. The catalyst is prepared in the manner of Example 1 of US Pat. No. 5,082,956. See WO 95/21225, for example, Example 1 and the specification thereof. The product is a slightly branched olefin, isomerized in its main structure having a range of chain lengths suitable for producing an alkylbenzenesulfonate surfactant for incorporation into a consumer cleaning composition. More generally, the temperature in this step can be from about 200 ° C to about 400 ° C, preferably from about 230 ° C to about 320 ° C. The pressure is typically from about 103 kPa to about 13788 kPa (15-2000 psig), more preferably from about 103 kPa to about 6895 kPa (15-1000 psig), more preferably from about 103 kPa to about 4137 kPa (15-600 psig). Hydrogen is a useful pressurizing gas. The space velocity (LHSV or WHSV) suitably is from 0.05 to approximately 20. Low pressure and low space velocity per hour provide improved selectivity, more isomerization and less cracking. The distillation to remove any volatile substance is by boiling up to 40 ° C / 10 mmHg.

Step (b): Alkylation of the product from step (a) using an aromatic hydrocarbon To a glass autoclave lining is added 1 mole equivalent of the highly branched olefin mixture produced in step (a), 20 mol equivalents of benzene and 20% by weight, based on the olefin mixture, of a shape-selective zeolite catalyst (acid mordenite catalyst Zeocat ™ FM-8 / 25H). The glass liner is sealed inside a stainless steel oscillating autoclave. The autoclave is purged twice with N2 at 1724 kPa (250 psig) and then charged at 6895 kPa (1000 psig) of N2. With mixing, the mixture is heated at 170-190 ° C for 14-15 hours, at which time it is then cooled and removed from the autoclave. The reaction mixture is filtered to remove the catalyst and concentrated by distilling off unreacted starting materials and / or impurities (eg benzene, olefin, paraffin, trace materials, with useful materials that are recycled without desired) to obtain a clear, almost colorless liquid product. The product is then formed into a desirable interrupted crystallinity surfactant system which can be transported, as an option, to a remote manufacturing facility where additional sulfonation and incorporation steps in consumer cleansing compositions can be carried out.

Stage (c): Sulfonation of the product of stage (b) The product of step (b) is sulfonated with one equivalent of chlorosulfonic acid using methylene chloride as the solvent. The methylene chloride is distilled off.

Stage (d): Neutralization of the product of stage (c) The product of step (c) is neutralized with sodium methoxide in metal and the methanol is evaporated to provide an interrupted crystallinity surfactant system.

EXAMPLE 2 Surface interrupted crystallinity surfactant system prepared via straight olefin isomerized in its main structure The procedure of Example 1 is repeated with the exception that the sulphonation step (c) uses sulfur trioxide (without methylene chloride solvent) as a sulfonating agent. The details of the sulfonation using a suitable mixture of air / sulfur trioxide is provided in US 3,427,342 Chemithon. In addition, step (d) uses sodium hydroxide instead of sodium methoxide for neutralization. EXAMPLE 3 Surfactant crystalline surfactant system prepared via straight olefin isomerized in its main structure Stage (a): At least partial reduction of the linearity of an olefin A highly branched olefin mixture is prepared by passing a mixture of C11, C12 and C13 monoolefins in a weight ratio of 1: 3: 1 over H-ferrite catalyst at 430 ° C. The method and catalyst of US 5,510,306 can be used for this step. The distillate removes any volatile by boiling up to 40 ° C / 10 mmHg. Step (b): Alkylation of the product of step (a) using an aromatic hydrocarbon To a glass-lined autoclave is added 1 mole equivalent of the highly branched olefin mixture of step (a), 20 mole equivalents of benzene and 20% by weight, based on the olefin mixture, of a selective zeolite catalyst. of form (acid mordenite catalyst ZeocatMR FM-8 / 25H). The glass liner is sealed inside a stainless steel oscillating autoclave. The autoclave is purged twice with 1724 kPa (250 psig) of N2, and then loaded with 6895 kPa (1000 psig) of N2. When mixing, the mixture is heated at 170-190 ° C overnight for 14-15 hours, at which time it is then cooled and removed from the autoclave. The reaction mixture is filtered to remove the catalyst. The benzene is distilled and recycled, the volatile impurities are also removed. A transparent colorless or almost colorless liquid product is obtained.

Stage (c): Sulfonation of the product of stage (b) The product of step (b) is sulfonated with one equivalent of chlorosulfonic acid using methylene chloride as the solvent. The methylene chloride is removed by distillation.

Stage (d): Neutralization of the product of stage (c).

The product of step (c) is neutralized with sodium methoxide in methanol and the methanol is evaporated to provide an interrupted crystallinity surfactant system of a sodium salt mixture.

EXAMPLE 4 Surfactant crystalline surfactant system prepared via isomerization in its main paraffin structure Stage (a i) A mixture of n-undecane, n-dodecane, n-tridecane, 1: 3: 1 by weight, is isomerized on Pt-SAPO-11 for a conversion of less than 90% at a temperature of about 300-340 ° C to 6895 kPa (1000 psig) under hydrogen gas, with a space velocity per hour by weight in the range of 2/3 and 30 moles of H2 / mole of hydrocarbon. Additional details of such isomerization are provided by S.J. Miller in Microporous Materials, Vol. 2., (1994), 439-449. In the additional examples the straight initial paraffin mixture can be the same as that used in the conventional LAB process. It is subjected to distillation to remove any volatile substance that boils up to 40 ° C / 10 mmHg.

Stage (a ii) The paraffin of step (a i) can be hydrogenated using conventional methods. See, for example, US 5,012,021, 4/30/91 or US 3,562,797, 2/9/71. The suitable dehydrogenation catalyst is any of the catalysts described in US 3,274,287; 3,315,007; 3,315,008; 3,745,112; 4,430,517 and 3,562,797. For the purposes of the present example, dehydrogenation is in accordance with US 3,562,797. The catalyst is zeolite A. The dehydrogenation is carried out in the vapor phase in the presence of oxygen (paraffin: 1: 1 molar dioxygen). The temperature is in the range of 450 ° C-550 ° C. The ratio of catalyst grams to total feed moles per hour is 3.9.

Step (b): Alkylation of the product of step (a) using an aromatic hydrocarbon To a glass-lined autoclave is added 1 mole equivalent of the mixture of step (a), 5 mole equivalents of benzene and 20% by weight, based on the olefin mixture, of a zeolite-selective catalyst ( acid mordenite catalyst Zeocat ™ FM-8 / 25H). The glass liner is sealed inside a stainless steel oscillating autoclave. The autoclave is purged twice with 1724 kPa (250 psig) of N2 and then charged at 6895 kPa (1000 psig) of N2. With the mixing, the mixture is heated at 170-190 ° C overnight for 14-15 hours, at which time it is then cooled and removed from the autoclave. The reaction mixture is filtered to remove the catalyst. Benzene and any paraffin that has not reacted are distilled and recycled. A transparent colorless or almost colorless liquid product is obtained.

Stage (c): Sulfonation of the product of stage (b) The product of step (b) is sulfonated with sulfur peroxide / air without using solvent. See US 3,427,342. The molar ratio of sulfur trioxide to alkylbenzene is from about 1.05: 1 to about 1.15: 1. The reaction stream is cooled and separated from the excess of sulfur trioxide.

Stage (d): Neutralization of the product of stage (c) The product of step (c) is neutralized with a slight excess of sodium hydroxide to provide an interrupted crystallinity surfactant system.

EXAMPLE 5 Surfactant crystallinity surfactant system prepared via a specific tertiary alcohol mixture from a Grignard reaction A mixture of 5-methyl-5-undecanol, 6-methyl-6-dodecanol and 7-methyl-7-tridecanol is prepared via the Next reaction from Grignard. A mixture of 28 g of 2-hexanone, 28 g of 2-heptanone, 14 g of 2-octanone and 100 g of diethyl ether is added to an addition funnel. The ketone mixture is then added dropwise over a period of 1.75 hours in a three neck round bottom flask, with stirring equipment and to which a nitrogen purge is applied, and placed with a reflux condenser and contains 350 ml of hexylmagnesium bromide 2.0 M in diethyl ether and an additional 100 ml of diethyl ether. After the addition is complete, the reaction mixture is stirred for an additional 1 hour at 20 ° C. The reaction mixture is then added to 600 g of a mixture of ice and water, with stirring. To this mixture is added 228.6 g of a 30% sulfuric acid solution. The two resulting liquid bases are added to a separating funnel. The aqueous layer is drained and the remaining ether layer is washed twice with 600 ml of water. The ether layer is then evaporated under vacuum to provide 115.45 g of the desired alcohol mixture. A 100 g sample of a light yellow alcohol mixture is added to a glass-lined autoclave together with 300 ml of benzene and 20 g of a shape selective zeolite catalyst (acid mordenite catalyst Zeocat R FM-8) / 25H). The glass lining is sealed inside the oscillating stainless steel autoclave. The autoclave is purged twice with 1724 kPa (250 psig) of N2 and then charged with 6895 kPa (1000 psig) of N2. With mixing, the mixture is heated at 170 ° C overnight, for 14-15 hours, in which time it is then cooled and removed from the autoclave. The reaction mixture is filtered to remove the catalyst and concentrated by distillation of the benzene which is dried and recycled. A slightly colorless or almost colorless transparent slightly branched olefin mixture is obtained. 50 g of the slightly branched olefin mixture which is provided by dehydrating the Grignard alcohol mixture as above is added to a glass-lined autoclave together with 150 ml of benzene and 10 g of zeolite-selective catalyst. (acid mordenite catalyst ZeocatMR FM-8 / 25H). The glass lining is sealed inside a stainless steel oscillating autoclave. The autoclave is purged twice with 1724 kPa (250 psig) of N2 and then charged with 6895 kPa (1000 psig) of N2. With mixing, the mixture is heated at 195 ° C overnight, for 14-15 hours, at which time it is then cooled and removed from the autoclave. The reaction mixture is filtered to remove the catalyst and concentrated by distilling off the benzene which is dried and recycled. A transparent colorless or almost colorless liquid product is obtained. The product is distilled under vacuum (1-5 mmHg) and the fraction of 95 ° C-135 ° C is retained. The fraction that is retained, ie, the colorless transparent or colorless liquid product, is then sulfonated with one molar equivalent of SO 3 and the resulting product is neutralized with sodium methoxide in methanol and the methanol is evaporated to provide a surfactant system of interrupted crystallinity PROOF OF TEMPERATURE OF CRITICAL SOLUBILITY OR TEST CST The critical solubility temperature test is a measure of the critical solubility temperature of a surfactant system. The temperature of critical solubility, said simply, is a measure of the temperature of a surfactant system at which the solubility increases suddenly and remarkably. This temperature becomes more important with current trends at increasingly lower wash temperatures. It has surprisingly been found that the critical solubility temperature of the alkylarylsulfonate surfactant system of the present invention can be lowered by the number and type of interrupted crystallinity alkylaryl sulfonate surfactants present in the alkylarylsulfonate surfactant system. The temperature of critical solubility is measured as follows: Glass equipment is used that is carefully cleaned and dried. All temperatures are measured using a calibrated mercury thermometer. The sample weights used are based on the anhydrous form of the solid surfactant or the surfactant mixture. A) Critical Sodium Solubility Temperature - An amount of 99 g of deionized water is weighed into a clean, dry beaker equipped with a magnetic stirrer. The beaker is then placed in an ice-water bath until the deionized water has cooled to 0 ° C. A 1.0 g sample of the solid sodium salt of the surfactant or of the surfactant mixture for which the critical sodium solubility temperature is to be measured is then added. The resulting heterogeneous solution is stirred for one hour. If the surfactant sample dissolves in the next hour and without any heating to provide a homogeneous and transparent solution, the critical solubility temperature of sodium is recorded as < 0 ° C. If the surfactant sample does not dissolve in the next hour to provide a clear homogenous solution, the heterogeneous solution is heated slowly with stirring at a rate of 0.1 ° C per minute. The temperature at which the surfactant sample is dissolved to provide a clear homogeneous solution is recorded as the temperature of critical sodium solubility. B) Critical Calcium Solubility Temperature - An amount of 99 g of deionized water is weighed into a clean, dry beaker, equipped with a magnetic stirrer. The beaker is then placed in an ice-water bath until the deionized water has cooled to 0 ° C. Then a 1.0 g sample of the solid calcium salt of the surfactant or the surfactant mixture for which the critical calcium solubility temperature is to be measured is added. The resulting heterogeneous solution is stirred for one hour. If the surfactant sample dissolves in the next hour and without any heating to provide a clear homogenous solution, the critical calcium solubility temperature is recorded as < 0 ° C. If the surfactant sample does not dissolve in the next hour to provide a clear homogenous solution, the heterogeneous solution is heated slowly with stirring at a rate of 0.1 ° C per minute. The temperature at which the surfactant sample is dissolved to provide a clear homogeneous solution is recorded as the temperature of critical calcium solubility. The sodium salts of the surfactant mixtures herein are the most common forms in which the surfactant mixtures are used. The conversion to calcium salts by simple metathesis, for example in diluted solution or aided by a suitable organic solvent, is well known. PROOF MODIFIED SCAS This method is an adaptation of the semicontinuous activated sludge process of the Soap and Detergent Association (SCAS) to determine the primary biodegradation of alkylbenzene sulfonate. The method involves exposing the chemical to relatively high concentrations of microorganisms for a prolonged period of time (possibly several months). The viability of the microorganisms is maintained during this period by the daily addition of a sedimentary wastewater feed. This modified test is also a standard OECD test for inherent biodegradability or 302A. This test was adopted by the OECD on May 12, 1981. The details of the "unmodified" SCAS test can be found in "A procedure and Standards for Alkylate Sulphonate", Journal of the American Oil Chemists "Society, Vol 42, p 986 (1965) The results obtained with the test for the surfactant or the surfactant system indicate that it has a high potential for biodegradation, and that for this reason is more useful as an inherent biodegradability test.The aeration units are identical to those described in the "unmodified" SCAS tests, that is, a Plexiglas pipe of 83 mm (3 1/4 inches) of Dl (diameter internal) tapered at the lower end 30 ° to the vertical to 13 mm (1/2 inch) hemisphere at the bottom, at a distance of 25.4 mm (1 inch) above the vertical wall joint and the The bottom of a 25.4 mm (1 inch) diameter opening for insertion of the air supply pipe is located, the total length of the aeration chamber must be at least 600 mm (24 inches). Optional draining can be placed at the 500 ml level for faci litar sampling. The units are left open to the atmosphere. The air is supplied to the aeration units from a small-scale laboratory air compressor. The air is filtered through glass wool or any other suitable means to remove contamination, oil, etc. The air is also pressurized with water to reduce the evaporation losses of the unit. The air is supplied at a rate of 500 ml / minute (3 ft3 / hour). The air is supplied via a capillary tube of 8 mm OD (outer diameter), 2 mm of Dl. The end of the capillary tube is located 7 mm (1/4 inch) from the bottom of the aeration chamber.

SACS Modified Test - The aeration units are cleaned and fixed in a suitable support. This procedure is carried out at 25 ° + 3 ° C. Concentrated solutions of the test surfactant or surfactant system are prepared: the required concentration is normally 400 mg / liter, since the organic carbon normally provides a concentration of test surfactant or surfactant system of 20 mg / liter of carbon at the beginning of each cycle of biodegradation if biodegradation does not occur. A sample of mixed liquor is obtained from the activated sludge plant to treat predominantly domestic sewage. Each aeration unit is filled with 150 ml of mixed liquor and aeration is started.

After 23 hours, the aeration stops, and the sludge is allowed to settle for 45 minutes. 100 ml of the supernatant liquor are extracted. A sample of domestic sewage is collected immediately before use, and 100 ml is added to the remaining sludge in each aeration unit. Aeration starts again. At this stage, no test materials are added and the units are fed daily with domestic sewage only until a transparent supernatant liquor is obtained when sedimenting. This usually requires up to two weeks, at which time the organic carbon dissolved in the supernatant liquor at the end of each aeration cycle must be less than 12 mg / liter. At the end of this period, the individual sedimented sludge is mixed and 50 ml of the resulting composite sludge is added to each unit. 100 ml of the sedimented sludge is added to the aeration units which will be the control units. Add 95 ml of sedimented wastewater plus 5 ml of the appropriate test surfactant or surfactant system, in concentrated solution (400 mg / l) to the aeration units which will be the control units. Aeration starts again and continues for 23 hours. The sludge is then allowed to settle for 45 minutes and the supernatant is extracted and analyzed to determine the content of dissolved organic carbon. The carbon content (D.O.C.) is analyzed using a SHIMADZU model TOC-5000 TOC analyzer. This filling and extraction procedure is repeated daily during the test. Before sedimentation it may be necessary to clean the walls of the units to avoid the accumulation of solids above the liquid level. A separate scraper or brush is used for each unit, to avoid cross-contamination. Ideally, dissolved organic carbon in the supernatant liquors is determined daily, although a less frequent analysis is permissible. Prior to analysis, the liquors are filtered through 0.45 micron membrane filters washed and centrifuged. The temperature of the sample does not exceed 40 ° C while it is in the centrifuge. The results of dissolved organic carbon in the supernatant liquors of the test aeration units and the control aeration units are plotted against time. To the extent that biodegradation is obtained, the level found in the test aeration units will approximate that found in the control aeration units. Once it is found that the difference between the two levels is constant with respect to the three consecutive measurements, three additional measurements are made and the percentage of biodegradation of the test surfactant or the surfactant system is calculated by the following equation:% biodegradation = Ot where OT = concentration of the test surfactant or surfactant system as organic carbon added to the sedimented sewage at the beginning of the aeration period. Ol = concentration of loose organic carbon found in the supernatant liquor of the test aeration units and at the end of the aeration period. Oc = concentration of dissolved organic carbon found in the supernatant liquor of the control aeration units. Therefore, the level of biodegradation is the percentage of removal of organic carbon. This modified test provides the following data (as reported on page 7 of the standard OECD test for inherent biodegradability, or 302 A) for tetrapropylenebenzene sulfonate ('TPBS': see "Surfactant Science Series", Vol. 56, Marcel Dekker, NY, 1996, page 43): CLEANING COMPOSITIONS The cleaning compositions of the present invention encompass a wide range of consumer cleaning product compositions that include powders, liquids, granules, gels, pastes, tablets, sacks, bars, types supplied in double-compartment containers, spray or foaming detergents. and other forms of homogenous or multi-phase consumer cleaning products. They can be used or applied manually and / or can be applied by unitary or freely alterable dosing, or by an automatic supply means, or are useful in devices such as washing machines or dishwashers or can be used in context of institutional cleaning including, for example, personal cleaning in public facilities for cleaning jars, for cleaning surgical instruments or for cleaning electronic components. They may also have a wide range of pH, for example from about 2 to about 12 or greater, and may have a wide range of alkalinity reserve which may include very high alkalinity reserves as in uses for example in the unblocking of drainage in which may be present tenths of a gram of NaOH equivalents per 100 grams of formulation, ranging from 1-10 grams of NaOH equivalents and moderate or low alkalinity ranges of liquid hand cleaners, down to the acidic side such as in acid cleaners on hard surfaces. Both types of high foaming and low foaming detergents are covered. Consumer product cleaning compositions are described in "Surfactant Science Series", Marcel Dekker, New York, Volumes 1-67 et seq. The liquid compositions in particular are described in detail in volume 67, "Liquid Detergents", Ed. Kuo-Yann Lai, 1997, ISBN 0-8247-9391-9 incorporated herein by reference. More classic formulations are described, especially granular types in "Detergent Manufacture including Zeolite Builders and Other New Materials", Ed. M. Sittig, Noyes Data Corporation, 1979 incorporated by reference. See also Kirk Othmer's Encyclopedia of Chemical Technology. Consumer product cleaning compositions herein include, but are not limited to: Light duty liquid detergents (LDL): these compositions include LDL compositions having a surfactant that enhances magnesium ions (see, for example WO 97/00930 A GB 2,292,562 A; US 5,376,310; US 5,269,974; US 5,230,823; US 4,923,635; US 4,681; 704; US 4,316,824; US 4,133,779) and / or organic diamines and / or various foam stabilizers and / or foam reinforcements such as amine oxides (see for example US 4,133,779) and / or skin sensation modifiers of surfactant, emollient and / or Enzyme types that include proteases; and / or antimicrobial agents; the most comprehensive patent lists are provided in Surfactant Science Series, volume 67, pages 240-248. Heavy Duty Liquid Detergents (HDL): These compositions include what are called so-called "structured" or multi-phase types of liquids (see for example US 4,452,717, US 4,526,709, US 4,530,780, US 4,618,446, US 4,793,943, US 4,659,497, US. 4,871, 467, US 4,891, 147, US 5,006,273, US 5,021, 195, US 5,147,576, US 5,160,655) and "unstructured" or isotropic liquids and in general can be aqueous or non-aqueous (see, for example, EP 738,778 A; 97/00937 A, WO 97/00936 A, EP 752,466 A, DE 19623623 A, WO 96/10073 A, WO 96/10072 A, US 4,647,393, US 4,648,983, US 4,655,954, US 4,661, 280, EP 225,654, US 4,690,771. US 4,744,916, US 4,753,750, US 4,950,424, US 5,004,556, US 5,102,574, WO 94/23009, and may be with bleach (see, for example, US 4,470,919, US 5,250,212, EP 564,250, US 5,264,143, US 5,275,753, US 5,288,746, 94/11483; EP 598,170; EP 598,973; EP 619,368; US 5,431,848; US 5,445,756) and / or enzymes (see, for example, US 3,944,470; 4,111, 855; US 4,261, 868; US 4,287,082; US 4,305,837; US 4,404,115; US 4,462,922; US 4,529,5225; US 4,537,706; US 4,537,707; US 670,179; US 4,842,758; US 4,900,475; US 4,908,150; US 5,082,585; US 5,156,773; WO 92/19709; EP 583,534; EP 583,535; EP 583,536; WO 94/04542; US 5,269,960; EP 633,311; US 5,422,030; US 5,431,842; US 5,442,100) or without bleach and / or enzymes. Other patents related to heavy duty liquid detergents are tabulated or included in Surfactant Science Series, Volume 67, pages 309-324.

Heavy Duty Granular Detergents (HDG): These compositions include both what are called "compacts" or agglomerates, or dried other than by spray, as well as what are termed "spongy" or spray-dried types . Phosphate and non-phosphate types are included. Such detergents may include the types based on the most common anionic surfactants or may be so-called "highly nonionic surfactant" types in which the nonionic surfactant is commonly held in or on an absorbent such as zeolites or other porous inorganic salts. The manufacture of HDG, for example, is described in EP 753,571 A; WO 96/38531 A; US 5,576,285; US 5,573,697; WO 96/34082 A; US 5,569,645; EP 739,977 A US 5,565,422; EP 737,739 A; WO 96/27655 A; US 5,554,587; WO 96/25482 A WO 96/23048; WO 96/22352 A; EP 709,449 A; WO 96/09370 A; US 5,496,487 US 5,489,392 and EP 694,608 A. "Softergents" (STW): these compositions include various granular or liquid types (see for example EP 753,569 A, US 4,140,641, US 4,639,321, US 4,751, 008, EP 315,126, US 4,844,821; 4,844,824; US 4,873,001; US 4,911,852; US 5,017,296; EP 422,787) of the types softened by washing the product and in general may have organic (for example quaternary) or inorganic (for example clays) softeners. Hard Surface Cleaners (HSC): these compositions include general purpose cleaners such as cream cleaners and general purpose liquid cleaners; general-purpose spray cleaners include glass and tile cleaners, and whitening spray cleaners; bathroom cleaners that include mold removers, which contain bleaches, antimicrobials, acid, neutral and basic types. See, for example EP 743,280 A; EP 743,279 A. Acid cleaners include those of WO 96/34938 A. Bar Soaps (BS &HW): these compositions include personal cleansing bars as well as what are referred to as laundry rods (see, for example WO 96/35772 A ); which includes types of soaps based on synthetic and soap-based detergents, and types with softener (see US 5,500,137 or WO 96/01889 A), such compositions may include those made by common soap-making techniques such as bar extrusion and / or the more unconventional techniques such as die-cutting, absorption of surfactant in a porous support or the like. Other bar soaps are also included (see for example BR 9502668, WO 96/04361 A, WO 96/04360 A, US 5,540,852). Other detergents for hand washing include those as described in GB 2,292,155 A and WO 96/01306 A.

Shampoos and conditioners (S &C): (see for example WO 96/37594 A, WO 96/17917 A, WO 96/17590 A, WO 96/17591 A). Such compositions generally include both simple shampoos and those referred to as "two in one" or conditioner types. Liquid Soaps (LS): these compositions include what are called "antibacterial" and conventional types, as well as those with or without skin conditioners and include types suitable for use in pumping supply and by any other means for example with fixed devices to the wall used institutionally. Fabric Softeners (FS): these compositions include the types both conventional liquid and liquid concentrate (see for example EP 754,749 A, WO 96/21715 A, US 5,531, 910, EP 705,900 A, US 5,500,138) as well as the types with dryer added or with support substrate (see, for example, US 5,562,847; US 5,559,088; EP 704,522 A). Other fabric softeners include solids (see, for example, US 5,505,866). Special Purpose Cleaners (SPC) include dry cleaning systems for home (see, for example WO 96/30583 A; WO 96/30472 A; WO 96/30471 A; US 5,547,476; WO 96/37652 A); pretreatment products with bleach for dirty laundry (see EP 751, 210 A); pretreatment products for fabric care (see, for example EP 752,469 A); types of liquid detergent for fine fabrics especially of the variety with high foaming; rinse aids for dishwashers; liquid whiteners that include both the chlorine type and the oxygen bleach type, and disinfectants, mouthwashes, denture cleansers (see, for example WO 96/19563 A; WO 96/19562 A), cleaners for vehicles or carpets or shampoos (see, for example EP 751, 213 A; WO 96/15308 A), hair rinses, shower gels, foam baths and personal care cleaners (see, for example WO 96/37595 A; WO 96/37592 A; WO 96/37591 A; WO 96/37589 A; WO 96/37588 TO; GB 2,297,975 A; FB 2,297,762 A; GB 2,297,761 A; WO 96/17916 A; WO 96/12468 A) and metal cleaners; as well as cleaning aids such as bleach builders and "dirt bar" or other types of pretreatment including special foam type cleaners (see, for example EP 753,560 A; EP 753,559 A; EP 753,588 A; EP 753,557 A; EP 753,556 A) and treatments against fading by the sun (see WO 96/03486 A, WO 96/03481 A; WO 96/03369 A) are also included. Detergents with long-lasting perfume (see for example US 5,500, 154, WO 96/02490) are becoming increasingly popular.

MATERIALS AND METHODS DETERGING IMPROVERS FOR LAUNDRY OR CLEANING The cleaning compositions of the present invention contain from about 0.00001% to about 99.9% by weight of at least one cleaning builder material which is selected from the group consisting of: i) detersive enzymes, which are preferably selected from proteases, amylases , lipases, cellulases, peroxidases and mixtures thereof; ii) organic detergent builders, • which are preferably selected from polycarboxylate compounds, 5-hydroxypolycarboxylate ether, substituted ammonium salts of polyacetic acids and mixtures thereof; iii) an oxygen bleaching agent, which is preferably selected from hydrogen peroxide, but inorganic hydrates, peroxo organic hydrates and organic peroxyacids, including hydrophilic and hydrophobic mono- and di-peroxyacids, and mixtures thereof same; V) bleach inactivators, which are preferably selected from TAED, NOBS and mixtures thereof; v) transition metal bleach catalysts, preferably bleach catalysts containing manganese; vi) oxygen transfer agents and precursors; vii) polymeric soil release agents; viii) soluble ethoxylated amines in water that have clay grime removal and anti-redeposition properties; ix) polymeric dispersing agents; x) polymeric agents • dye transfer inhibitors; xi) alkoxylated polycarboxylates; and xii) mixtures thereof. In general, a laundry or cleaning assistant is any The material needed to transform a composition containing only the minimum essential ingredients into a composition useful for laundry or cleaning purposes. In preferred embodiments, laundry detergent or cleaning improvers are readily recognizable by those skilled in the art that are absolutely characteristic of laundry or cleaning products, especially laundry or cleaning products designed for direct use by a consumer in a domestic environment The precise nature of these additional components and the levels of incorporation thereof will depend on the physical form of the composition and the nature of the cleaning operation for which it is to be used. Preferably, the detergency builder ingredients if used with bleach should have good stability therewith. Certain detergent compositions herein must be boron-free and / or phosphate-free as required by legislation. The levels of detergency builders are from about 0.0001% to about 99.9%, typically from about 70% to about 95% by weight of the compositions. The levels of use of the total compositions can vary widely based on the proposed application, and vary, for example from some ppm in solution to what is termed "direct application" of the pure cleaning composition to the surface to be cleaned. . Common builders include detergency builders, surfactants, polymers, bleaches, bleach activators, catalytic materials and the like excluding any material that is already defined above as part of the essential component of the compositions of the invention. Other detergency builders herein may include various active ingredients or specialized materials such as dispersant polymers (e.g. from BASF Corp. or Rohm & amp;; Haas), stains of color, agents for the care of silver, against tarnishing and / or anticorrosion, dyes, fillers, germicides, alkalinity sources, hydrotropes, antioxidants, enzyme stabilizing agents, properfumes, perfumes, solubilizing agents, carriers, processing aids, pigments and, for liquid formulations, solvents as described in detail in the following. Most typically, the laundry or cleansing compositions herein such as laundry detergents, laundry detergent builders, hard surface cleaners, synthetic and soap based laundry bars, fabric softeners and liquid treatments for fabrics, solids and treatment articles of all kinds will require several detergency builders, although some simply formulated products, such as bleach builders may require only, for example, an oxygen bleaching agent and a surfactant as described in this document. A comprehensive list of suitable laundry detergent builders or cleaners and methods can be found in U.S. Provisional Patent Application number 60 / 053,319 filed July 21, 1997 and assigned to Procter & Gamble.

Detersive Surfactants - The present compositions desirably include a detersive surfactant. Detersive surfactants are illustrated extensively in U.S. 3,929,678, December 30, 1975 Laughlin et al., And U.S. 4,259,217, March 31, 1981, Murphy; in the series "Surfactant Science", Marcel Dekker, Inc., New York and Basel; in "Handbook of Surfactants", M.R. Porter, Chapman and Hall, 2nd Ed ,. 1994; in "Surfactants in Consumer Products", Ed. J. Falbe, Springer-Verlag, 1987; and in numerous patents related to detergents ceded to Procter & Gamble and other manufacturers of detergent and consumer products. The detersive surfactant herein therefore include the anionic, nonionic, amphoteric or amphoteric types of surfactant known for use as textile laundry cleansing agents, but do not include completely foam-free or completely insoluble surfactants (although these may be used as optional detergency builders). Examples of the type of surfactant considered optional for the present purposes are relatively uncommon compared to the cleaning surfactants, but include, for example, common fabric softening materials such as dioctadecyldimethylammonium chloride. In more detail, detersive surfactants useful herein typically at levels of about 1% to about 55% by weight suitably include: (1) conventional alkylbenzene sulfonates; (2) olefinsulfonates, which includes α-olefinsulfonates and sulfonates derived from fatty acids and fatty esters; (3) alkyl or alkenyl sulfosuccinates, including diester and half ester types as well as sulfosuccinates and other types of sulfonate carboxylate surfactants such as sulfosuccinates derived from ethoxylated alcohols and alkanolamides; (4) paraffin or alkanesulfonate- and alkyl or alkenylcarboxisulfonate, types including the product of addition of bisulfite to α-olefins; (5) alkylnaphthalenesulfonates; (6) alkyl isethionates and alkoxypropanesulfonates; as well as esters of fatty isethionate, fatty esters of ethoxylated isethionate and other ester sulfonates such as the 3-hydroxypropanesulfonate ester or the AVANEL S types: (7) benzene, eumeno, toluene, xylene and naphthalenesulfonates, useful especially for their hydrotropic properties; (8) alkyl ether sulfonates; (9) alkylamide sulfonates; (10) fatty a-sulfoacids salts or esters and sulfoacids internal esters; (11) alkyl glyceryl sulfonates; (12) ligninsulfonates; (13) petroleum sulfonates, sometimes known as heavy alkylate sulfonates; (14) diphenyl oxide disulfonates; (15) linear or branched alkyl or alkenyl sulfates; (16) alkyl or alkylphenolalkoxylate sulphates and the corresponding polyalkoxylates, sometimes known as alkyl ether sulphates, as well as alkenyl alkoxy sulfates or alkenyl polyalkoxysulfates; (17) alkylamide sulfates or alkenyl amides sulfates, including sulphated alkanolamides and their alkoxylates and polyalkoxylates; (18) sulphated oils, sulphated alkyl glycerides, sulfated alkyl polyglycosides or sulfated sugar derived surfactants; (19) alkylalkoxycarboxylates and alkylpolyalkoxycarboxylates including salts of galacturonic acid; (20) alkyl ester carboxylates and alkenylester carboxylates; (21) alkyl or alkenylcarboxylates, especially conventional soaps and a, β-dicarboxylates, which also include alkyl- and alkenyl succinates; (22) alkyl or alkenyl amidoalkoxy- and polyalkoxy carboxylates; (23) types of alkyl and alkenylamidocarboxylate surfactant, including sarcosinates, taurides, glycinates, amidopropionates and imidopropionates; (24) amide soaps sometimes referred to as fatty acid cyanamides; (25) alkylpolyaminocarboxylates; (26) phosphorus-based surfactants which include alkyl or alkenyl phosphate esters, alkyl ether phosphates including their alkoxylated derivatives, salts of phosphatidic acid, salts of alkyl phosphonic acid, alkyldi (polyoxyalkylene alkanol) phosphates, amphoteric phosphates such as lecithins; and phosphate / carboxylate, phosphate / sulfate and phosphate / sulfonate types; (27) nonionic surfactants of the Pluronic and Tetronic type; (28) the so-called EO / PO block polymers, which include the types of diblock and triblock EPE and PEP; (29) fatty acid polyglycol esters; (30) ethoxylated alkyl or alkylphenol capped or unroofed, propoxylates and butoxylates including fatty alcohol polyethylene glycol ethers; (31) fatty alcohols, especially when they are useful as viscosity modifying surfactants or present as unreacted components of other surfactants; (32) N-alkyl polyhydroxy fatty acid amides, especially alkyl N-alkylglucamides; (33) nonionic surfactants derived from mono- or polysaccharides or sorbitan, especially alkyl polyglycosides as well as fatty acid esters of sucrose; (34) ethylene glycol-, propylene glycol-, glycerol- and polyglyceryl esters and their alkoxylates, especially glycerol ethers and the fatty acids / glycerol monoesters and diesters; (35) aldobionamide surfactants; (36) type of nonionic alkylsulccinimide surfactant; (37) acetylenic alcohol surfactants, such as SURFYNOLS; (38) alkanolamide surfactants and their alkoxylated derivatives including fatty acid alkanolamides and fatty acid polyglycol ether alkanolamides; (39) alkylpyrrolidones; (40) alkylamine oxides, including alkoxylated or polyalkoxylated amine oxides and amine oxides derived from sugars; (41) alkylphosphinoxides; (42) sulfonide surfactants; (43) amphoteric sulfonates, especially sulfobetaines; (44) amphoteric betaine type, including types derived from aminocarboxylate; (45) amphoteric sulfates such as alkylammonium polyethoxy sulfates; (46) alkylamines and amine salts derived from fats and petroleum; (47) alkylimidazolines; (48) alkylamidoamines and their alkoxylated and polyalkoxylate derivatives; and (49) conventional cationic surfactants that include water-soluble alkyltrimethylammonium salts. In addition, more types of non-usual surfactants are included such as: (50) alkylamidoaminoxides, carboxylates and quaternary salts; (51) sugar-derived surfactants modeled after any of the other conventional sugar-free types mentioned above; (52) Fluorosurfactants; (53) biotensive agents; (54) organosilicon surfactants; (55) gemini surfactants, other than the diphenyloxide disulfonates mentioned above, which include those derived from glucose; (56) polymeric surfactants including amphiphilcarboxyglycinates; and (57) ballform surfactants. With respect to the conventional alkylbenzene sulfonates indicated above, especially for substantially straight types including those produced using alkylation by AICI3 or HF, suitable chain lengths are from about C10 to about C14. Such linear alkylbenzene sulphonate surfactants may be present in the present compositions either as a result of being prepared separately and in combination, or as results of being present in one or more precursors of the essential surfactants of interrupted crystallinity. The ratios of the straight alkylbenzene sulfonates and of the present invention of interrupted crystallinity can vary from 100: 1 to 1: 100; more typically, when alkylbenzene sulfonates are used, a fraction of at least about 0.1 percent, preferably a fraction of at least about 0.25 by weight, which is the interrupted crystallinity surfactant of the present invention. In any of the above detersive surfactants, the hydrophobic chain length is typically in the general range of C8-C20, with chain lengths in the range of C8-C18 often being preferred, especially when the laundry process is to be carried out. in cold water. The selection of chain lengths and the degree of alkoxylation for conventional purposes are described in standard texts. When the detersive surfactant is a salt, any compatible cation, including H (that is, the acid or partially acid form of a potentially acidic surfactant can be used), Na, K, Mg, ammonium or alkanolammonium or combinations of the cations can be present. Mixtures of detersive surfactants having different charges are commonly preferred, especially, anionic / cationic, anionic / nonionic, anionic / nonionic / cationic, anionic / nonionic / amphoteric, nonionic / cationic and nonionic / amphoteric mixtures. In addition, any single detersive surfactant can be substituted, often with desirable results for washing in cold water, by mixtures of otherwise similar detersive surfactants having chain lengths, degree of unsaturation or branching, degree of alkoxylation (especially ethoxylation) , insertion of substituents such as oxygen atoms in the different hydrophobes, or any combination thereof. Preferred among the detersive surfactants identified above are: linear C9-C20 alkylbenzenesulfonates of acid, sodium and ammonium, particularly C10-C15 alkyl linear secondary sodium benzenesulfonates (1); olefinsulfonate salts (2), that is, material made by reacting olefins, particularly C10-C20 α-olefins, with sulfur trioxide and then neutralizing and hydrolysing the reaction product; sodium and C7-C12 ammonium dialkylsulfosuccinates, (3); alkane monosulfonates (4), such as the derivatives by reacting C8-C20 α-olefins with sodium bisulfite and those derived by reacting paraffins with SO2 and Cb and then hydrolyzing with a base to form a random sulfonate; salts or esters of fatty a-sulfoacid, (10); sodium alkyl glyceryl sulfonates, (11), especially those ethers of higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; alkyl or alkenyl sulfates, (15), which may be primary or secondary, saturated or unsaturated, branched or unbranched. Such compounds, when branched, can be random or regular. When they are secondary they preferably have the formula CH3 (CH2) x (CHOSO3-M +) CH3 or CH3 (CH2) and (CHOSO3-M +) CH2CH3 where x and (y +1) are integers of at least 7, preferably at least minus 9, and M is a cation soluble in water, preferably sodium. When unsaturated, sulfates such as oleum sulfate are preferred, while sodium and ammonium alkyl sulfates, especially those produced by sulfating C8-C18 alcohols, produced for example from tallow or from coconut oil are also useful; also preferred are alkyl or alkenyl ether sulphates, (16), especially ethoxysulfates having about 0.5 mole or more of ethoxylation, preferably 0.5-8; alkyl ether carboxylates, (19), especially EO 1-5 ethoxycarboxylates; soaps or fatty acids (21), preferably the most water-soluble types; the amino acid type surfactants, (23), such as sarcosinates, especially oleylsarcosinate; phosphate esters, (26); alkyl or alkylphenol ethoxylates, propoxylates and butoxylates, (30), especially the ethoxylates "AE", which include the so-called narrow-chain alkyl ethoxylates and alkylphenol C6-C12 ethoxylates as well as the straight or branched primary C8-C18 alcohols or secondary aliphatics with ethylene oxide, generally 2-30 EO; N-alkyl polyhydroxy fatty acid amides especially C12-C18 N-methylglucamides (32), see WO 9206154 and N-alkoxy polyhydroxy fatty acid amides such as C10-C18 N- (3-methoxypropyl) glucamide while glucamides can be used of C12-C18 from N-propyl to N-hexyl for little sudsing; alkyl polyglycosides (33); amine oxides, (40), preferably alkyldimethyleneamine N-oxides and their dihydrates; sulfobetaines or "sultaines", (43); betaines (44); and gemini surfactants. Suitable levels of anionic detersive surfactants herein are in the range of from about 1% to about 50% or greater, preferably from about 2% to about %, more preferably from about 5% to about % by weight of the detergent composition. Suitable levels of nonionic detersive surfactant herein are from about 1% to about 40%, preferably from about 2% to about 30%, more preferably from about 5% to about 20%. Desirable weight ratios of anionic: nonionic surfactants in combination include from 1.0: 9.0 to 1.0: 0.25, preferably 1.0: 1.5 to 1.0: 0.4. Suitable levels of cationic detersive surfactant herein are from about 0.1% to about 20%, preferably from about 1% to about 15%, although much higher levels, for example up to about 30% or greater, may be useful, especially in non-ionic formulations: cationic (ie, limited or anionic free). Amphoteric or zwitterionic detersive surfactants, when present, are usually useful at levels in the range of about 0.1% to about 20% by weight of the detergent composition. Frequently the levels will be limited to approximately 5% or less, especially when the amphoteric is expensive.

DETERSIVE ENZYMES Enzymes are preferably included in the present detergent compositions for various purposes, including the removal of stains from protein-based substrates, based on carbohydrates or based on triglycerides, for the prevention of refuge dye transfer in fabric laundry processes and for the restoration of fabrics. Recent descriptions of enzymes in the detergents useful herein include combinations of bleach / amylase / protease (EP 755,999 A, EP 756,001 A, EP 756,000 A), chondriotinase (EP 747,469 A); Protease variants (WO 96/28566 A, WO 96/28557 A, WO 96/28556 A, WO 96/25489 A); xylanase (EP 709.452 A); keratinase (EP 747,470 A); lipase (GB 2,297,979 A; WO 96/16153 A; WO 96/12004 A; EP 698,659 A; WO 96/16154 A); cellulase (GB 2,294,269 A; WO 96/27649 A; GB 2,303,147 A); termitase (WO 96/28558 A). More generally, suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, xylanases, keratinases, chondriotinases; termitases, curtinases and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, mycotic and yeast origin. Preferred selections are altered by factors such as pH of activity and / or optimum stability, thermostability and stability to active ingredients, builders and the like. In this regard, bacterial or mycotic enzymes, such as bacterial amylases and proteases, and fungal cellulases are preferred. Suitable enzymes are also described in US Patent Nos. 5,677,272, 5,679,630, 5,703,027, 5,703,034, 5,705,464, 5,707,950, 5,707,951, 5,710,115, 5,710,116, 5,710,118, 5,710,119 and 5,721,202. As used herein, the term "detersive enzyme" means any enzyme that has a cleaning, stain remover or otherwise beneficial effect in laundry, hard surface cleaning or a personal care detergent composition. Preferred detersive enzymes are hydrolases such as proteases, amylases and lipases. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases and peroxidases. Amylases and / or proteases are widely preferred, including both commercially available standard types and improved types which, although more and more compatible with bleach by successive improvements, have a remaining degree of susceptibility to bleach deactivation. Enzymes are normally incorporated in detergent or detergent additive compositions at levels sufficient to provide an "effective cleaning amount". The term "effective cleaning amount" refers to any amount capable of cleaningRemoval of stains, removal of dirt, bleached, deodorized or freshness enhancing effect on substrates such as fabrics, frets and the like. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg of active enzyme per gram of the detergent composition. Stated otherwise, the compositions herein will typically comprise from 0.001% to 5%, preferably 0.01% -1% by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide 0.005 to 0.1 Anson units (AU) of activity per gram of composition. For certain detergents it may be desirable to increase the active enzyme content of the commercial preparation in order to minimize the total amount of non-catalytically active materials and thereby improve stain / film removal or other final results. Higher active levels may also be desirable in highly concentrated detergent formulations. Suitable examples of proteases are subtilisins which are obtained in particular from strains of B. subtilis and β. licheniformis. A suitable protease is a Bacillus strain that has a maximum activity through the pH range of 8-12, developed and sold as ESPERASEMR by Novo Industries A / S of Denmark, then "Novo". The preparation of this enzyme and analogous enzymes are described in GB 1, 243,784 for Novo. Other suitable proteases include ALCALASEMR and SAVINASEMR from Novo and MAXATASEMR from International Bio-Synthetics, Inc., The Netherlands; as well as Protease A described in EP 130,756 A, January 9, 1985 and protease B as described in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. See also a high pH protease of Bacillus sp. NCIMB 40338 described in WO 9318140 A for Novo. Enzymatic detergents comprise protease, one or more other enzymes and a reversible protease inhibitor are described in WO 9203529 A for Novo. Other preferred proteases include those of WO 9510591 for Procter & Gamble. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 9507791 for Procter & Gamble. A recombinant trypsin-like protease for detergents suitable herein is disclosed in WO 9425583 for Novo. In more detail, an especially preferred protease, referred to as "protease D" is a variant of carbonylhydrolase having an amino acid sequence that is not found in nature, which is derived from a precursor carbonylhydrolase by substituting a different amino acid for a plurality. of amino acid residues at a position in the carbonylhydrolase equivalent to the +76 position, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104 , +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, + 217, +218, +222, +260, +265 and / or +274 according to the subtilisin numbering of Bacillus amyloquefaciens as described in WO 95/10615 published on April 20, 1995 by Genencor International. Useful proteases are also described in PCT publications: WO 95/30010 published November 9, 1995 by Procter & Gamble; WO 95/30011 published November 9, 1995 by Procter & Gamble; WO 95/29979 published November 9, 199 by Procter & Gamble. Amylases suitable herein include, for example, α-amylases described in GB 1, 296, 839 for Novo; RAPIDASEMR, International Bio-Synthetics, Inc. and TERMAMYLMR Novo. FUNGAMYLMR from Novo is especially useful. Enzyme engineering is known for improved stability, for example, oxidative stability. See, for example J. Biological Chem., Vol. 260, No. 11, June 1985, p. 6518-6521. Certain preferred embodiments of the present compositions may make use of amylases having improved stability in detergents, especially improved oxidative stability measured against the TERMAMYL reference point in commercial use in 1993. These preferred amylases herein share the characteristic of being amylases of "enhanced stability" characterized, at a minimum by a measurable improvement in one plus: oxidative stability, for example, to hydrogen peroxide / tetraacetylethylene diamine in buffered solution at pH 9-10; thermal stability, for example, at common wash temperatures such as about 60 ° C; or alkaline stability, for example at a pH of about 8 to about 11, measured versus the amylase of the reference point identified above. The stability can be measured using any of the technical tests described in the art. See, for example, references described in WO 9402597. Amylases of increased stability can be obtained from Novo or Genencor International. A class of highly preferred amylases herein have in common to be derived using site-directed mutagenesis of one or more of the Bacillus amylases, especially Bacillus α-amylases, regardless of whether one, two or multiple amylase strains are the precursors. immediate. Oxidative amylases of increased stability versus the aforementioned reference amylases are preferred for use, especially in bleaching, more preferably in bleaching with oxygen, other than bleaching detergent compositions with chlorine, at the moment. Preferred amylases include: (a) an amylase according to WO 9402597, incorporated above, Novo, February 3, 1994, as further illustrated by a mutant in which substitution is performed, using alanine or threonine, preferably threonine, from the methionine residue located at position 197 of the B. licheniformis amylase, known as TERMAMYLMR, or the variation in the homologous position of a similar parental amylase, such as B. amyloliquefaciens, B. subtilis or B. stearothermophilus; (b) amylases with improved stability, as described by Genencor International in a document entitled Oxidatively Resistant alpha-Amylases "presented at the 207th American Chemical Society National Meeting, March 13-17 1994, by C. Mitchinson. Note that bleaching in automatic dishwashing detergents inactivates alpha-amylases but amylases with improved oxidative stability have been developed by Genencor from ß. licheniformis in NCIB8061.Methionine (Met) is identified as the most likely residue to be modified. Met is substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants, of which particularly important is M197L and M197T, with the variant M197T as the variant expressed Stability is measured in CASCADEMR and SUNLIGHTMR, (c) particularly preferred amylases herein include amylase variants having further modification in the immediate parental as described in WO 9510603 A and are available from the assignee, Novo, as DURAMYL R. Another amylase with enhanced oxidative stability, particularly preferred, includes that described in WO 9418314 for Genencor International and WO 9402597 for Novo. Any other amylase with increased oxidative stability can be used, for example as derived by site-directed mutagenesis from chimeric, hybrid or single mutant parental forms of available amylases. Other preferred enzyme modifications are accessible. See WO 9509909 A for Novo. Other amylase enzymes include those described in WO 95/26397 and in the co-pending application by Novo Nordisk PCT / DK96 / 00056. Specific amylase enzymes for use in the detergent compositions of the present invention include α-amylases characterized by having a specific activity at least 25% greater than the specific activity of Termamyl R in a temperature range of 25 ° C to 55 ° C and at a pH value in the range of 8 to 10, as measured by the α-amylase activity assay of Phadebas ™ (Such a α-amylase activity assay of Phadebas ™ is described on pages 9-10, WO 95/26397) . Also indicated herein are α-amylases which are at least 80% homologous to the amino acid sequences shown in the SEC lists. FROM IDENT. in the references. These enzymes are preferably incorporated in the laundry detergent compositions at a level of 0.00018% to 0.060% pure enzyme by weight of the total composition, more preferably from 0.00024% to 0.048% pure enzyme by weight of the total composition. The cellulases used herein include both bacterial and fungal types, preferably having an optimum pH between 5 and 9.5. US 4,435,307, Barbesgoard et al, March 6, 1984, describes suitable fungal cellulases of Humicola insolens or Humicola strain DSM1800 or a cellulase-producing fungus 212 belonging to the genus Aeromonas and cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella Atrium Solander Suitable cellulases are also described in GB-A-2,075,028; GB-A-2,095,275 and DE-OS-2,247,832. CAREZYMEMR and CELLUZYMEMR (Novo) are especially useful. See also WO 9117243 for Novo. Lipase enzymes suitable for detergent use include those produced by microorganisms of the Pseudomonas group such as Pseudomonas stutzeri ATCC 19,154, as described in GB 1, 372, 034. See also lipases in Japanese patent application 53,20487, open to the public on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya., Japan, under the trade name Lipase P "Amano" , or "Amano-P". Other suitable commercial lipases include the Amano-CES lipases from Chromobacter viscosum, for example Chromobacter viscosum variety lipoliticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., E.U.A. and Disoynth Co., The Netherlands, and lipases from Pseudomonas gladioli. The LIPOLASEMR enzyme derived from Humicola lanuginosa and commercially available from Novo, see also EP 341, 947, is a preferred lipase for use herein. Variants of lipase and amylase stabilized against peroxidase enzymes are described in WO 9414951 A for Novo. See also WO 9205249 and RD 94359044. Cutinase enzymes suitable for use herein are described in WO 8809367 A for Genencor. The peroxidase enzymes can be used in combination with oxygen sources, for example, percarbonate, perborate, hydrogen peroxide, etc. for "solution bleaching" or prevention of transfer of dyes or pigments removed from substrates during washing to other substrates present in the washing solution. Known peroxidases include horseradish peroxidases, ligninase, and haloperoxidases such as chloro- or bromo-peroxidase. Peroxidase-containing detergent compositions are described in WO 89099813 A, October 19, 1989 for Novo and WO 8909813 A for Novo.

A range of enzymatic materials and means for their incorporation into synthetic detergent compositions are also described in WO 9307263 A and WO 9307260 A for Genencor International, WO 8908694 A for Novo and US 3,553,139, January 5, 1971 for McCarty et al. Enzymes are further described in US 4,101, 457, Place et al, July 18, 1978 and in US 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid formulations of detergents and their incorporation into such formulations are describe in US 4,261, 868, Hora et al., April 14, 1981. Enzymes for detergent use can be stabilized by various techniques. Enzyme stabilization techniques are described and exemplified in US 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, in US 3,519,570. A useful Bacillus sp AC13 provides proteases, xylanases and cellulases and is described in WO 9401532 for Novo.

DETERGENT IMPROVERS Detergent builders of the detergents are preferably included in the compositions herein, for example, to help control mineral hardness, especially Ca and / or Mg in the wash waters or to aid in the removal and / or suspension. of particulate grime from surfaces and sometimes to provide alkalinity and / or damping action. In solid formulations, builders sometimes serve as absorbers for surfactants. Alternatively certain compositions can be formulated with binders completely soluble in water, either organic or inorganic, depending on the proposed use. Suitable silicate builders include water soluble and hydrous solid types and include those having a chain, layer or three dimensional structure as well as solid amorphous silicates or other types, for example, those specially adapted for use in liquid detergents unstructured Preferred are alkali metal silicates, particularly those liquids and solids having an SiO2: Na2O ratio in the range of 1.6: 1 to 3.2: 1, including hydrous solid 2-silicates ratio sold by PQ Corp. under the trade name BRITESIL R, for example BRITESIL H2O; and stratified silicates, for example those described in US 4,664,839, May 12, 1987, H.P. Rieck NaSKS-6, sometimes abbreviated "SKS-6", is an aluminum-free, crystalline layered d-Na2SiOs morphology silicate sold by Hoechst is especially preferred in granular laundry compositions. See the preparative methods in the German document DE-A-3, 417,649 and DE-A-3, 742,043. Other layered silicates, such as those having the general formula NaMSiXO2x + 1.yH2O wherein M is sodium or hydrogen, X is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0. , also, or alternatively they may be used in the present. The layered silicates of Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-11 and silicate forms layered a, β and β - Other silicates may also be useful, such as magnesium silicate, which can serve as an agent undulatory in granules, as a stabilizing agent for bleaches and as a component for foaming control systems. Also suitable for use herein are crystalline ion exchange materials synthesized or hydrates thereof having a chain structure and a composition represented by the following general formula in an anhydrous form: xM2O and SiO2zM'O wherein M is Na and / or K, M 'is Ca and / or Mg; y / x is 0.5 to 2.0 and z / x is 0.005 to 1.0 as described in US 5,427,711, Sakaguchi et al, June 27, 1995. Aluminosilicate builders, such as zeolites, are especially useful in granular detergents, but they can also be incorporated in liquids, pastes or gels. Suitable for the present purpose are those that have the empirical formula: [Mz (A1O2) z (SiO2) v] -xH2O where z and v are integers of at least 6, the ratio of zav is in the range of 1.0 to 0.5 and x is an integer from 15 to 264. Aluminosilicates may be crystalline or amorphous, occurring naturally or synthetically derived. An aluminosilicate production method is found in 3,985,669, Krummel, et al. Oct. 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials are available as Zeolite A, Zeolite P (B), Zeolite X and, to whatever degree it differs from zeolite P, what is termed zeolite MAP.

Natural types that include clinoptilolite can be used. Zeolite A has the formula: Na? [(A1 O2)? 2 (SiO2)? 2]. XH2O where x is from 20 to 30, especially 27. Dehydrated zeolites (x = 0-10) can also be used.

Preferably, the aluminosilicate has a particle size of 0.1-10 microns in diameter. Detergent builders, instead of or in addition to the silicates and aluminosilicates described above, may optionally be included in the compositions herein, for example, to help control mineral hardness, especially Ca and / or Mg. , in wash water or to assist in the removal of particulate dirt from surfaces. The detergency builders can operate via various mechanisms that include the formation of soluble or insoluble complexes with hardness ions, by ion exchange and by offering a more favorable surface for the precipitation of hardness ions compared to the surfaces of articles that they are going to be cleaned. The level of builder can vary widely depending on the final use and the physical form of the composition. Detergent builder detergents typically comprise at least about 1% builder. Liquid formulations typically comprise about 5% to about 50% more typically, 5% to 35% builder. Granular formulations typically comprise from about 10% to about 80%, more typically 15% to 50%, detergent builder by weight of the detergent composition. Minor or higher levels of builders are not excluded. For example, certain detergent additives or formulations with high surfactant capacity may be without builders. Suitable detergency builders herein may be selected from the group consisting of phosphates and polyphosphates, especially the sodium salts; carbonates, bicarbonates, sesquicarbonates and mineral carbonates other than sodium carbonate or sesquicarbonate; organic mono-, di-, tri- and tetracarboxylates, especially water-soluble non-surfactant carboxylates in the form of an acid, sodium, potassium or alkanolammonium salt, as well as water-soluble oligomeric polymer or low molecular weight carboxylates, which include aliphatic and aromatic types and phytic acid. This can be complemented by borates, for example for buffering purposes or by sulfates, especially sodium sulfate and any other filler or carrier which may be important for the engineering of a stable surfactant and / or detergent compositions containing builders. detergency The builder mixtures sometimes referred to as "builder systems" can be used and typically comprise two or more conventional builders, optionally supplemented by chelators, pH buffers or fillers, although the latter materials are generally considered separately when describing the quantities of materials in them. In terms of relative amounts of surfactant and builder in the present detergents, preferred builder systems are typically formulated in a weight ratio of surfactant to builder of from about 60: 1 to about 1: 80. Certain preferred laundry detergents have a ratio in the range of 0.90: 1.0 to 4.0: 1.0, more preferably 0.95: 1.0 to 3.0: 1.0. P-containing detergent buffers are often preferred when allowed by legislation and include, but are not limited to, alkali metal, ammonium and alkanolammonium salts of polyphosphates exemplified by tripolyphosphates, pyrophosphates, vitreous polymeric meta-phosphates; and phosphonates. Suitable carbonate builders include alkaline earth metal and alkali metal carbonates as described in German Patent Application No. 2, 321, 001 published November 15, 1973, although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate and other mineral carbonates such as trona or any convenient multiple salt of sodium carbonate and calcium carbonate such as those having the composition 2Na2CO.3.CaC03, when they are anhydrous, and even calcium carbonates including calcite, aragonite and vaterite, especially forms having high surface areas relative to compact calcite, may be useful, for example as seeds for use in synthetic detergent bars. Suitable "organic detergent builders", as described herein for use with the alkylarylsulfonate surfactant system, include polycarboxylate compounds that include water-soluble non-surfactant dicarboxylates and tricarboxylates. More typically, the builder polycarboxylates have a plurality of carboxylate groups, preferably at least 3 carboxylates. The carboxylate builders can be formulated in acid, partially neutral, neutral or base form. When they are in salt form, alkali metals, such as sodium, potassium and lithium or alkanolammonium salts are preferred. Polycarboxylate builders include ether polycarboxylates such as oxide disuccinate, see Berg, US 3,128,287, April 7, 1964 and Lamberti et al, US 3,635,830, January 18, 1972.; detergency builders "TMS / TDS" of US 4,663,071, Bush et al, May 5, 1987; and other ether carboxylates including cyclic and alicyclic compounds such as those described in US Pat. No. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. Other suitable organic detergent builders are ether hydroxypolycarboxylates, maleic anhydride copolymers with ethylene or vinyl methyl ether; 1, 3, 5-trihydroxybenzene-2,4,6-trisulfonic acid; carboxymethyloxysuccinic acid; the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid; as well as mellitic acid, succinic acid, polymaleic acid, benzene, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrates, for example citric acid and soluble salts thereof are important carboxylate builders, for example, for heavy duty liquid detergents due to the availability of renewable resources and biodegradability. The citrates can also be used in granular compositions, especially in combination with zeolite and / or layered silicates. Oxydisuccinates are also especially useful in such compositions and combinations. When allowed, and especially in the formation of bars used for hand washing operations, alkali metal phosphates such as sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane 1-hydroxy-1,1-diphosphonate or other known phosphonates, for example those of US 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137 may also be used and may have desirable antifouling properties. Certain detersive surfactants or their short chain counterparts also have detergency builder action. For purposes of consideration of an unambiguous formula, when they have tensioactive capacity, these materials are added as detersive surfactants. Preferred types of detergency builder functionality are illustrated by: 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds described in US 4,566,948, Bush, January 28, 1986. The detergency builders of Succinic acid include C5-C20 alkyl and alkenyl succinic acids and salts thereof. Succinate builders also include: lauryl succinate, myristiisuccinate, palmitiisuccinate, 2-dodecenylsuccinate (preferred), 2-pentanodecenylsuccinate and the like. Lauryl succinates are described in European patent application 86200690.5 / 0,200,263, published on November 5, 1986. Fatty acids, for example C12-C18 monocarboxylic acids can also be incorporated into the compositions as surfactants / builders alone or in combination with the detergency builders mentioned above, especially citrate and / or succinate builders to provide additional builder activity. Other suitable polycarboxylates are described in US 4,144,226, Crutchfield et al, March 13, 1979 and US 3,308,067, Diehl, March 7, 1967. See also Diehl, US 3,723,322. Other types of inorganic builders materials which can be used have the formula (Mx) i Cay (CO3) z where xei are integers from 1 to 15, and is an integer from 1 to 10, z is a number whole from 2 to 25, Mi are cations, at least one of which is soluble in water, and the equation? i = 1-15 (xi multiplied by the valence of Mi) + 2y = 2z is satisfied so that the Formula has a neutral or "balanced" charge. These detergency builders are referred to herein as "mineral builders", examples of these detergency builders and their use and preparation can be found in US Pat. No. 5,707,959. Another suitable class of inorganic builders is the magnesiosilicates, see WO97 / 0179.

OXYGEN BLEACHING AGENTS Preferred compositions of the present invention comprise, as part or all of the laundry adjuvant or cleanser materials, an "oxygen bleaching agent". The oxygen bleaching agents useful in the present invention can be any of the known oxidizing agents for laundry, hard surface cleaners, for automatic dishwashing or for denture cleaning purposes. Oxygen bleaches or mixtures thereof are preferred, although other oxidizing bleaches, such as oxygen, an enzyme hydrogen peroxide producing system, or hypoalites such as chlorine bleaches such as hypochlorite can also be used. Common oxygen bleaches of the peroxygen type include hydrogen peroxide, inorganic peroxohydrates, but organic alcohols and organic peroxyacids, which include hydrophilic and hydrophobic mono- or di-peroxyacids. These may be peroxycarboxylic acids, peroxyidic acids, amidoperoxycarboxylic acids or their salts which include the calcium, magnesium or mixed cation salts. Percents of various kinds can be used in both free form and precursors known as "bleach activators" or "bleach promoters" which, when combined with a source of hydrogen peroxide, are hydrolyzed to release the corresponding peracid. Also useful in the present are oxygen bleaches which are inorganic peroxides such as Na 2 O 2, superoxides such as KO 2, organic hydroperoxides such as eumeno hydroperoxide, and t-butyl hydroperoxide and the inorganic peroxyacids and their salts such as peroxysulfuric acid salts, especially the potassium salt of peroxydisulfuric acid, most preferably peroxomonosulfuric acid and including the commercial triple salt form sold by OXONE by DuPont and also any commercially available equivalent of such forms as CUROX from Akzo and CAROAT from Degussa. Certain organic peroxides, such as dibenzoyl peroxide, may be useful, especially as additives instead of as primary oxygen bleach. Mixed oxygen bleach systems are generally useful, as they are mixtures of any oxygen bleach with the known bleach activators, organic catalysts, enzyme catalysts and mixtures thereof.; In addition, such mixtures may include also brighteners, photobleaches and dye transfer inhibitors of the types well known in the art. Preferred oxygen bleaches, as indicated, include peroxohydrates, sometimes known as peroxyhydrates or peroxohydrates. These are organic or, more commonly, inorganic salts capable of easily releasing hydrogen peroxide. Peroxohydrates are the most common examples of "hydrogen peroxide source" materials and include perborates, percarbonates, perfosphates and persilicates. Suitable peroxohydrates include sodium carbonate peroxyhydrate and the commercial equivalent of "percarbonate" bleaches, and any of the so-called sodium perborate hydrates, with "tetrahydrate" and "monohydrate" being preferred; although sodium pyrophosphate peroxyhydrate can be used. Many such peroxohydrates are available in processed forms with coatings, such as silicate and / or borate and / or serous materials and / or surfactants, or have particle geometries such as compact spheres, which improve storage stability. By means of organic peroxohydrates, urea peroxohydrate may also be useful herein. Percarbonate bleaches include, for example, dry particles having an average particle size in the range of about 500 microns to about 1,000 microns, no greater than about 10% by weight of the particles are smaller than about 200 microns. , and no more than about 10% by weight of the particles are greater than about 1.250 microns. Percarbonates and perborates are widely available commercially, for example from FMC, Solvay and Tokai Denka. The organic percarboxylic acids useful herein as oxygen bleach include magnesium monoperoxyphthalate hexahydrate, available from Interox, m-chloroperbenzoic acid and its salts 4-nonylamino-4-oxoperoxybutyric acid and diperoxydecanedioic acid and their salts. Such bleaches are described in US 4,483,781, US Patent Application 740,446, Burns, et al, filed June 3, 1985, EP-A 133,354, published February 20, 1985 and US 4,412,934. The organic percarboxylic acids usable herein include those which contain one, two and more peroxy groups and may be aliphatic or aromatic. Highly preferred oxygen bleaches also include 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as described in 4,634,551. A comprehensive and comprehensive list of useful oxygen bleaches including inorganic peroxohydrates, organic peroxohydrates and organic peroxyacids including mono- or di-peroxyacids, hydrophilic or hydrophobic peroxycarboxylic acids, peroxyimidic acids, amidoperoxycarboxylic acids or their salts, include the salts of calcium, magnesium or mixed cations, and can be found in US patents 5,622,646 and 5,686,014. Other percents and bleach activators useful herein are in the family of imidoperacids and imido bleach activators. These include phthaloylimidoperoxycaproic acid and the related derivatives substituted with arylimido and acyloxy nitrogen. For lists of such compounds, preparations and their incorporation into laundry compositions including both granules and liquids, see US 5,487,818; US 5,470,988, US 5,466,825; US 5,419,846; US 5,415,796; US 5,391, 324; US 5,328,634; US 5,310,934; US 5,279,757; US 5,246,620; US 5,245,075; US 5,294,362; US 5,423,998; US 5,208,340; US 5,132,431 and US 5,087,385. Useful diperoxy acids include, for example, 1,2-diperoxydecanedioic acid (DPDA); 1, 9-diperoxyazelaic acid; diperoxybrassilic acid; diperoxysebasic acid and diperoxyisophthalic acid; 2-decyliperoxybutane-1,4-dioic acid and 4,4'-sulfonylbisperoxybenzoic acid. More generally, the terms "hydrophilic" and "hydrophobic" used herein in connection with any of the oxygen bleaches, especially those killed and in relation to bleach activators, are in first stay based on whether the given oxygen bleach effectively bleach fugitive dyes in solution so it avoids gray coloring of fabric and discoloration and / or removes more hydrophilic stains such as tea, wine and grape juice - in the case it is called "hydrophilic". When the oxygen bleach or bleach activator has a significant removal of stains, on blackish, greasy, carotenoid or other hydrophobic dirt, it is called "hydrophobic". The terms are also applicable when referring to percents or bleach activators used in combination with a source of hydrogen peroxide. The current commercial reference points for the hydrophilic operation of oxygen bleaching systems are: TAED or peracetic acid, for reference point of hydrophilic bleach. NOBS or NAPAA are the corresponding reference points for hydrophobic bleach. The terms "hydrophilic" "hydrophobic" and "hydrotropic" with reference to oxygen bleaches include percents and here extend to a bleach activator that has also been used in some manner more closely in the literature. See especially Kirk Othmer's Encyclopedia of Chemical Technology, Vol. 4, pages 284-285. This reference provides a chromatographic retention time and a set based on criteria critical micelle concentration, and is useful for identifying and / or characterizing preferred subclasses of hydrophobic, hydrophilic and hydrotropic oxygen bleaches and bleach activators that can be used in the present invention.

BLEACH ACTIVATORS Bleach activators useful herein include amides, imides, esters and anhydrides. Commonly at least one substituted or unsubstituted acyl moiety is present, covalently connected to a leaving group as in the structure R-C (O) -L. In a preferred mode of use, the bleach activators are combined with a source of hydrogen peroxide, such as perborates or percarbonates, in a single product. Conveniently, the product only leads to an in situ production in aqueous solution (ie, during the washing process) of the percarboxylic acid corresponding to the bleach activator. The product itself can be hydrous, for example a powder, to the extent that the water is controlled in an amount and mobility so that storage stability is acceptable. Alternatively, the product may be an anhydrous solid or liquid. In another mode, the bleach activator or oxygen bleach is incorporated into a pretreatment product, such as a dirt bar; pretreated and dirtied substrates are then exposed to further treatments, for example from a source of hydrogen peroxide. With respect to the anterior bleach activator structure R (C (O) L, the atom in the leaving group which is connected to the acyl portion of the peracid formation R (C) 0- most typically is O or N The bleach activators may be uncharged, positively or negatively charged in peracid and / or uncharged portions, positively or negatively charged from the leaving groups One or more of the peracid forming moieties or leaving groups may be present. See, for example, US 5,595,957, US 5,561, 235, US 5,560,862 or the bis- (peroxy-carbonic) system of US 5,534,179 Mixtures of suitable bleach activators may also be used Whitening activators may be substituted with electroliberators or electroliberators, either in the leaving group or in the peracid forming portion or portions, changing their reactivity and rendering them more or less suitable for particular pH or washing conditions. For example, electroatracting groups such as NO2 improve the effectiveness of bleach activators designed for use under moderate pH wash conditions (e.g. from about 7.5 to about 9.5). A comprehensive and exhaustive description of suitable bleach activators and suitable leaving groups, as well as how to determine suitable activators, can be found in US Patents 5,686,014 and 5,622,646. Cationic bleach activators include the types of carbamate-quaternary, carbonate-quaternary, quaternary-ester and quaternary amide, providing a range of cationic peroxyimidic, peroxycarbonic or peroxycarboxylic acids to the wash. An analogous but non-cationic palette of bleach activators is available when quaternary derivatives are not desired. In more detail, the cationic activators include quaternary ammonium substituted activators of WO 96-06915, US 4,751, 015 and 4,397,757, EP-A-284292, EP-A-331, 229 and EP-A-03520. Cationic nitriles are also useful as described in EP-A-303,520 and in the European patent specification. 458,396 and 464,880. Other types of nitrile have electron-withdrawing substituents as described in US 5,591, 378. Other descriptions of bleach activator include GB 836,988; 864,798; 907,356; 1, 003,310 and 1, 519,351; German Patent 3,337,921; EP-A-0185522; EP-A-0174132; EP-A-0120591; and U.S. Patent Nos. 1, 246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393 and the phenol sulfonate alkanoylamino acid ester described in US 5,523,434. Suitable bleach activators include any type of acetylated diamine, whether hydrophilic or hydrophobic in nature. Of the above classes of bleach precursors, preferred classes include esters that include acyl phenols sulfonates, acylalkyl phenols sulfonates or acyloxybenzenesulfonates (leaving group OBS); the acylamides; the peroxyacid precursors substituted with quaternary ammonium including the cationic nitriles. Preferred bleach activators include N, N, N ', N'-tetraacetylethylenediamine (TAED) or any of its close relatives which include triacetyl or other asymmetric derivatives. TAED and acetylated carbohydrates such as glucose pentaacetate and tetraacetylxylose are preferred as hydrophilic bleach activators. Based on the application, acetiltrietilcitrato, a liquid, also has some utility, as well as phenylbenzoate. Preferred hydrophobic bleach activators include sodium nonanoyloxybenzenesulfonate (NOBS or SNOBS), N- (alkanoyl) aminoalkanoyloxybenzenesulfonates such as 4- [N- (nonaoyl) aminohexanoyloxy] -benzenesulfonate or (NACA-OBS) as described in US Patent 5,534,642 and in EPA 0 355 384 A1, the types of substituted amide described in detail in the following, such as activators related to NAPAA and activators related to certain imidoperacid bleach, for example as described in US Patent 5,061, 807 , granted on October 29, 1991 and assigned to Hoechst Aktiengesellschaft in Frankfurt, Germany and the application for patent open to the Japanese public (Kokai) No. 4-28799. Another group of peracids already activating herein are those derivable from acyclic imidoperoxycarboxylic acids and salts thereof, see US Pat. 5415796 and imidoperoxycarboxylic cyclic acids and salts thereof, see U.S. Pat. ,061,807, 5,132,431, 5,6542.69, 5,246,620, 5,419,864 and 5,438,147. Other suitable bleach activators include sodium-4-benzoyloxybenzenesulfonate (SBOBS); sodium-1-methyl-2-benzoyloxy-benzene-4-sulfonate; sodium-4-methyl-3-benzoyloxy benzoate (SPCC); trimethylammonium toluoyloxybenzenesulfonate; or sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (STHOBS). Bleach activators can be used in an amount of up to 20%, preferably 0.1-10% by weight of the composition, although higher levels of 40% or more are acceptable, for example, in highly concentrated bleach additive product forms. or forms designed for automated application dosing. The highly preferred bleach activators useful herein are substituted with amide and a comprehensive and exhaustive description of these activators can be found in US Patents. 5,686,014 and 5,622,646. Other useful activators, described in US 4,966,723, are of the benzoxazine type, such as a CeH ring to which a DC (O) OC (R1) = IM- portion is fused at positions 1, 2. A highly preferred activator of the benzoxazine type is: Based on the activator and precise application, good bleaching results can be obtained from bleaching systems having a usage pH of from about 6 to about 13, preferably from about 9.0 to about 10.5. Typically, for example, activators with electro-attractant properties are used for near-neutral or sub-neutral pH ranges. Alkaline agents and buffers can be used to ensure such a pH. Acyllactam activators are very useful herein, especially acylcaprolactams (see for example WO 94-28102 A) and acylvalerolactams (see US 5,503,639). See also. US 4,545,784 which describes acylcaprolactams which include benzoylcaprolactam adsorbed to sodium perborate. In certain preferred embodiments of the invention, NOBS, lactam activators, imide activators or amide-functional activators, especially the more hydrophobic derivatives, with hydrophilic activators such as TAED, typically in weight ratios of hydrophobic activator, are desirably combined. : TAED in the range of 1: 5 to 5: 1, preferably of approximately 1: 1. Other suitable lactam activators are modified in alpha, see WO 96-22350 A1, July 25, 1996. Lactam activators, especially of the more hydrophobic types, are desirably used in combination with TAED, typically in weight ratios. of activators derived with amido or caprolactam: TAED in the range of 1: 5 to 5: 1, preferably approximately 1: 1. See also bleach activators having a cyclic amidine leaving group described in US 5,552,556. Non-limiting examples of additional activators useful herein are to be found in US 4,915,854. US 4,412,934 and 4,634,551. The hydrophobic nonanoyloxybenzenesulfonate activator (NOBS) and the tetraacetylethylenediamine hydrophilic activator (TAED) are typical, and mixtures thereof may also be used. Additional activators useful herein include those of US 5,545,349.

TRANSITION METAL WHITENER CATALYSTS If desired, the bleaching compounds can be catalyzed by means of a manganese compound. Such compounds are well known in the art and include, for example, the manganese-based catalysts described in US Patent 5,246,621, US Patent 5,244,594; US patent 5,194,416; US patent 5,114,606; European public patent application Nos. 549,271 A1, 549,272A1, 544,440A2, 544,490A1; and applications PCT / IB98 / 00298 (attorney's file No. 6257X), PCT / IB98 / 00299 (attorney's file No. 6537), PCT / IB98 / 00300 (attorney's file No. 6525XL &) and PCT / IB98 / 00302 (attorney's file No. 6524L #); Preferred examples of these catalysts include MnlV2 (u-0) 3 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2 (PF6) 2, Mnlll2 (u-OAc) 2 (1, 4.7 -trimetiM, 4,7-triazacyclononane) 2 (PF6) 2, Mnlll2 (uO) -1 (u-OAc) 2 (1, 4, 7-trimethyl-1, 4,7-triazacyclononane) 2 (C104) 2, MnlV4 (u-0) 6 (1, 4,7-triazacyclononane) 4 (C104) 4, Mnlll-MnlV4 (uO) 1 (u-OAc) 2- (1, 4,7-trimethyl-1, 4,7 -triazacyclononane) 2 (C1O4) 3, MnlV (1, 4,7-trimethyl-1, 4,7-triazacyclononane) - (OCH 3) 3 (PF 6), and mixtures thereof. Other metal-based bleach catalysts include those described in US Patents. 4,430,243, 5,114,611, 5622,646 and 5,686,014. The use of manganese with various complex ligands to improve bleaching is also reported in the following United States patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084. The cobalt bleach catalysts useful herein are known and described, for example in M.L. Tobe, "Base Hydrolysis of Transition-Metal Complexes," Adv. Inorq. Bioinorq. Mech., (1983), 2, pages 1-94. The most preferred cobalt catalyst useful herein are cobalt pentaamine acetate salts having the formula [Co (NH3) 5OAc] Ty, wherein "OAc" represents a cetate moiety and "Ty" is an anion, and especially pentaamine chloride cobalt acetate [Co (NH3) 5OAc] C12; as well as [Co (NH3) 5OAc] (OAc) 2; [Co (NH3) 5OAc] (PF6) 2; [Co (NH3) 5OAc] (SO4); [Co (NH3) 5OAc] (BF4) 2; and [Co (NH3) 5OAc] (NO3) 2 (in the present "CAP"). These cobalt catalysts are easily prepared by known methods, such as those described, for example, in the Tobe article and the references mentioned therein, and in US Pat. No. 4,810,410, to Diakun et al, filed on March 7, 1989. The compositions herein may also suitably include as a bleaching catalyst the class of transition metal complexes of a macropolycyclic rigid ligand. The phrase "macropolicíclico rigid ligand" is sometimes abbreviated as "MRL". A useful MRL is [MnByclamC12], where "Bcyclam" is (5,12-dimetiM, 5,8,12-tetraazabicyclo [6.6.2] hexadecane). See applications PCT, PCT / IB98 / 00298 (attorney's file No. 6527X), PCT / IB98 / 00299 (attorney's file No. 6537), PCT / IB98 / 00300 (attorney's file No. 6525XL &) and PCT / IB98 / 00302 (attorney's file No. 6524L #). The amount used is a catalytically effective amount, suitably from about 1 ppb or greater, 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 (where "ppb" indicates parts per billion by weight and "ppm" indicates parts per million by weight). As a practical matter, and not meaning a limitation, the cleaning compositions and processes herein can be adjusted to provide in the order of one part per one hundred million active bleach catalyst species in the aqueous washing medium, and preferably will provide about 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm to about 10 ppm, and more preferably from about 0.1 ppm to about 5 ppm of the bleach catalyst species in the wash liquor. In order to obtain such levels in the wash liquor of an automatic washing process, typical compositions herein will comprise from about 0.0005% to about 0.2%, more preferably from about 0.004% to about 0.08% bleaching catalyst , especially manganese or cobalt catalysts, by weight of the cleaning compositions.

ENZYMATIC SOURCES OF HYDROGEN PEROXIDE In a different field than the bleach activators illustrated in the above, another suitable hydrogen peroxide generator system is a combination of a C1-C4 alkanoxydase and a C1-C4 alkanol, especially a combination of methanol oxidase (MOX) and ethanol . Such combinations are described in WO 94/03003. Other enzyme materials related to bleaching, such as peroxidases, haloperoxidases, superoxide bismucrases, catalases and their enhancers or, more commonly, inhibitors, can be used as optional ingredients in the present compositions.

AGENTS AND PRECURSORS OF OXYGEN TRANSFER Also useful herein are any of the known organic bleach catalysts, oxygen transfer agents or precursors thereof. These include the compounds themselves and / or their precursors, for example, any ketone suitable for the production of dioxiranes and / or any analogs of dioxirane precursors or dioxiranes containing heteroatoms, such as sulfonimines R1 R2C = NSO2R3, see EP 446 982 A, published in 1991 and sulfonyloxyazaridines, see EP 446,981 A, published in 1991. Preferred examples of such materials include hydrophilic or hydrophobic ketones, used especially together with monoperoxysulfates to produce dioxiranes in situ and / or the mines described in US 5,576,282 and the references described here. The oxygen bleaches preferably used in conjunction with oxygen transfer agents or precursors include percarboxylic acids and salts, percarbonic acids and salts, peroxymonosulfuric acid and salts, and mixtures thereof. See also US 5,360,568; US 5,360,569; US 5,370,826 and US 5,442,066. Although oxygen bleaching systems and / or their precursors may be susceptible to decomposition during storage in the presence of moisture, air (oxygen and / or carbon dioxide) and trace metals (especially oxides or simple salts or colloidal oxides of metals of transition) and when subjected to light, stability can be improved by adding common sequestrants (chelants) and / or polymeric dispersants and / or a small amount of antioxidant to the bleach system or product. See, for example, US 5,545,349. Antioxidants are often added to detergent ingredients and vary from enzymes to surfactants. Their presence is not necessarily inconsistent with the use of an oxidizing bleach; for example, the introduction of a phase barrier can be used to stabilize a seemingly incompatible combination of an enzyme and antioxidant, on the one hand, and an oxygen bleach, on the other. Although substances commonly known as antioxidants can be used, see for example US Patents. 5686014, 5622646, 5055218, 4853143, 4539130 and 4483778. Preferred antioxidants are 3,5-di-tert-butyl-4-hydroxytoluene, 2,5-di-tert-butylhydroquinone and D, L-alpha-tocopherol.

POLYMERIC RELEASE AGENT OF MUGRE The compositions according to the present invention optionally comprise one or more agents for release of dirt. The polymeric agents for release of dirt are characterized in that they have hydrophilic segments, to hydrophilize the surface of the hydrophobic fibers such as polyester and nylon, and hydrophobic segments, to deposit on hydrophobic fibers and remain adhered thereto upon completion of the washing cycle, and in this way, serve as an anchor for the hydrophilic segments. This may allow the grime that appears subsequent to the treatment with the grime-releasing agent to be more easily cleaned in subsequent washing processes. If used, the soil release agents generally comprise from about 0.01% to about 10%, preferably from about 0.1% to about 5%, and more preferably from about 0.2% to about 3% by weight of the composition. The following, all included herein by reference, describe suitable soil release polymers for use in the present invention. US 5,691, 298 Gosselink et al., Filed November 25, 1997; US 5,599,782 Pan et al., Filed February 4, 1997; US 5,415,807 Gosselink et al., Filed May 16, 1995; US 5,182,043 Morrall et al., Filed January 26, 1993; US 4,956,447 Gosselink et al., Filed September 11, 1990; US 4,976,879 Maldonado et al. • 10 filed on December 11, 1990; US 4,968,451 Scheibel et al., Filed November 6, 1990; US 4,925,577 Borcher, Sr. et al., Issued May 15, 1990; US 4,861, 512 Gosselink, filed August 29, 1989; US 4,877,896 Maldonado et al., Filed October 31, 1989; US 4,702,857 Gosselink et al., Filed on October 27, 1987; US 4,711, 730 Gosselink et al., Filed December 8, 1987; US 4,721, 580 Gosselink filed January 26, 1988; US 4,000,093 Nicol et • al., Filed on December 28, 1976; US 3,959,230 Hayes, filed May 25, 1976; US 3,893,929 Basadur, filed July 8, 1975; and European patent application 0 219 048, published on April 22, 1987 by Kud et al. Additional agents suitable for release of dirt are described in US 4,201, 824 Voilland et al .; US 4,240,918 Lagasse et al .; US 4,525,524 Tung et al .; US 4,579,681 Ruppert et al .; 4,220,918; US 4,787,989; EP 279,134 A, 1988 for Rhone-Poulenc Chemie; EP 457,205 A for BASF (1991) and DE 2,335,044 for Unilever N.V., 1974; all incorporated herein by reference.

AGENTS OF REMOVAL OF MUGRE DE ARCILLA / ANTI-REDEPOSICIÓN The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having clay grime removal and anti-redeposition properties. Granular detergent compositions which contain these compounds typically contain from about 0.01% to about 10.0% by weight of water-soluble ethoxylated amines; liquid detergent compositions typically contain about 0.01% to about 5%. A preferred agent for soil release and anti-redeposition is ethoxylated tetraethylene pentamine. Exemplary ethoxylated amines are further described in the US patent. 4,597,898, VanderMeer, filed July 1, 1986. Another group of preferred agents for clay-anti-redeposition soil removal are the cationic compounds described in European patent application 111, 965, Oh and Gosselink, published on 27 June 1984. Other clay removal / anti-redeposition agents which may be used include ethoxylated amine polymers described in European Patent Application 111, 984, Gosselink, published June 27, 1984; the zwitterionic polymers described in European patent application 112,592, Gosselink, published on July 4, 1984; and the amine oxides described in US Pat. No. 4,548,744, Connor, filed October 22, 1985. Other clay removal and / or anti redeposition agents known in the art can also be used in the compositions herein . See US Patent 4,891, 160 VanderMeer, filed on January 2, 1990 and WO 95/32272, published on November 30, 1995. Another type of preferred anti-redeposition agent includes carboxymethylcellulose (CMC) materials. These materials are well known in the art.

POLYMERIC DISPERSANT AGENTS Polymeric dispersing agents can advantageously be used at levels of from about 0.1% to about 7% by weight, in the compositions herein, especially in the presence of zeolite and / or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art may also be used. It is considered, although not intended to be limited by theory, that polymeric dispersing agents improve the overall performance of builders, when used in combination with other detergency builders (including lower molecular weight polycarboxylates) by inhibition of crystal growth, release of particulate dirt, peptization and anti-redeposition. The polycarboxylate polymeric materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids which can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the present polymeric polycarboxylates or the monomeric segments which do not contain carboxylate radicals such as vinylmethylether, styrene, ethylene, etc., is suitably provided so that the segments do not constitute more than about 40% by weight. Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein, are the water-soluble salts of 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 much more 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. The use of polyacrylates of this type in detergent compositions has been described, for example, in Diehl, US Patent 3,308,067, filed on March 7, 1967. Acrylic / maleic based copolymers can also be used as a preferred component of the dispersing agent / anti-redeposition. Such materials include 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 and much more preferably from about 7,000 to 65,000. The ratio of acrylate to maleate segments in such copolymers will generally vary from about 30: 1 to about 1: 1, more preferably from about 10: 1 to 2: 1. The water-soluble salts of such acrylic acid / maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. The soluble acrylate / maleate copolymers of this type are known materials which are described in European patent application No. 66915, published on December 15, 1982, as well as EP 193,360, published on September 3, 1986, which also describes such polymers comprising hydroxypropylacrylate. Other useful additional dispersing agents include the maleic / acrylic / vinyl alcohol terpolymers. Such materials are also described in EP 193,360, which include, for example, the terpolymer 45/45/10 of acrylic / maleic / vinyl alcohol. Another polymeric material which may be included is polyethylene glycol (PEG). The PEG can show an operation of dispersing agent and also act as an agent for removing its dirt from clay-anti-redeposition. Typical molecular weight ranges for this purpose range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000. The polyaspartate and polyglutamate dispersing agents can also be used, especially in conjunction with zeolite builders. Dispersing agents such as polyaspartate preferably have a molecular weight (average) of about ,000. Other types of polymer which may be more desirable for biodegradability, improved bleach stability or cleaning purposes include various hydrophobically modified terpolymers and copolymers including those sold by Rohm & Haas, BASF, Corp., Nippon Shokubai and others for all types of textile treatment, water treatment or detergent applications.

RINSE AID Any optical brightener or other brightening or whitening agents known in the art can be incorporated at typical levels from about 0.01% to about 1.2% by weight, in the detergent compositions herein, when designed for fabric washing or treatment. Specific examples of optical brighteners which are useful in the present compositions are those identified in the US patent. 4,790,856, awarded to Wixon on December 13, 1988. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners described in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Arctic White CC and Arctic White CWD, the 2- (4-styryl-phenyl) -2H-naphtho [1,2-d] triazoles; 4,4'-bis- (1, 2,3-triazol-2-yl) -stilbenes; 4,4'-bis (styryl) bisphenyl and aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethyl-amino coumarin; 1,2-bis (benzimidazol-2-yl) ethylene; 1,3-diphenyl-pyrazolines; 2,5-bis (benzoxazol-2-yl) thiophene; 2-styryl-naphtho [1,2-d] oxazole; and 2- (stilben-4-yl) -2H-naphtho [1,2] triazole. See also the US patent. 3,646,015, filed on February 29, 1972 for Hamilton.

POLYMERIC AGENTS INHIBITORS OF TRANSFER OF COLORANT The compositions of the present invention may also include one or more materials effective to inhibit the transfer of dyes from one fabric to another during the cleaning process. Generally, such dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxides and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%, and more preferably from about 0.05% to about 2%. Amine polymers N-oxides typically have an amine to amine N-oxide ratio of 10: 1 to 1: 1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer may vary by appropriate copolymerization or by an appropriate degree of N-oxidation. Polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferably from 1,000 to 500,000; and much more preferably from 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO". See U.S. Patent 5,633,255 to Fredj. The most preferred N-oxide polyamine useful in the detergent compositions herein are poly (4-vinylpyridine-N-oxide) which has an average molecular weight of about 50,000 and an amine N-oxide ratio of about 1: 4. Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as a class, such as "PVPVl") are also referenced for use herein. Preferably, PVPVl has an average molecular weight range of 5,000 to 1,000,000, more preferably 5,000 to 200,000 and much more preferably 10,000 to 20,000. (The average molecular weight range is determined by light scattering, as described in Barth, et al., Chemical Analysis, Vol. 113. "Modern Methods of Polymer Characterization," the descriptions of which are incorporated herein by reference. reference). PVPVl copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1: 1 to 0.2: 1, more preferably from 0.8: 1 to 0.3.1, more preferably from 0.6.1 to 0.4: 1. These copolymers can be linear or branched. The compositions of the present invention may also use a polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000 and more preferably from about 5,000 to about 50,000. PVPs are known to the experts in the field of detergents; see, for example EP-A-262,897 and EP-A-256,696, incorporated herein by reference. The compositions containing PVP may also contain polyethylene glycol ("PEG") having an average molecular weight of from about 500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP, on a ppm basis supplied in wash solutions is from about 2: 1 to about 50: 1 and more preferably from about 3: 1 to about 10: 1. The detergent compositions herein may also contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which may also provide a dye transfer inhibiting action. If used, the compositions herein will preferably comprise from about 0.01% to 1% by weight of such optical brighteners. The hydrophilic optical brighteners useful in the present invention include, for example, 4,4'-bis [(4-anilino-6- (N-2-bis-hydroxyeti -s-triazine-amino-4-a) stilbendisulfonic and the disodium salt (Tinopal-UNPA-GX), disodium salt of 4,4'-bis [(4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) ) amino] 2,2'-stilbenedisulfonic acid (Tinopal 5BM-GX) and the sodium salt of 4,4'-bis [(4-anilino-6-morpholino-s-triazine-2-yl) amino] 2,2 -stilbendisulfonic, (Tinopal AMS-GX) all by Ciba Geigy Corporation.The specific optical brightening species selected for use in the present invention provide benefits in the ability to inhibit effective transfer of dyes when used in combination with polymeric inhibitory agents. Selected dye transfer described so far The combination of such selected polymeric materials (eg PVNO and / or PVPVl) with such optical brighteners selected (for example Tinopal UNPA-GX, Tinopal 5BM-GX and / or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than either of these two components of detergent composition when used alone Without wishing to be bound by any theory, the extent to which the brighteners are deposited on fabrics in the wash solution can be defined by a parameter referred to as "depletion coefficient". The depletion coefficient is generally defined as the ratio of a) the polishing material deposited on the fabric to b) the initial concentration of polish in the wash liquor. Brighteners with relatively high depletion coefficients are most suitable for inhibiting the transfer of dyes in the context of the present invention. Other types of conventional optical brighteners may optionally be used in the present compositions to provide conventional fabrics with "brightness" benefits, rather than a dye transfer inhibiting effect. Such use is conventional and well known for detergent formulations.

CHELATING AGENTS The detergent compositions herein may optionally contain one or more chelating agents, particularly chelating agents for adventitious transition metals. Those commonly found in wash water include iron and / or manganese in water soluble, colloidal or particulate form, and may be associated as oxides or hydroxides, or they may be found in association with mugres such as unique substances. Preferred chelants are those which effectively control such transition metals, which include especially the control of the deposition of such transition metals or their compounds on ics and / or the control of undesired redox reactions in the washing medium and / or in the ic or in interfaces with hard surfaces. Such chelating agents include those having low molecular weights as well as those of polymeric types, which typically have at least 1, and preferably 2 or more donor heteroatoms such as O or N, capable of coordination with a transition metal. Common chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, all of which are defined in the following. Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethylenediaminetriacetates, nitrilotriacetates, ethylenediaminetetrapropionates, triethylenetetraaminehexaacetates, diethylenetriaminepentaacetates and ethanoldiglicines, their alkali metal, ammonium and substituted ammonium salts, and mixtures thereof. Aminophosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are allowed in detergent compositions and include ethylenediaminetetrakis (methylenephosphonates) such as DEQUEST.

Preferably, these amino phosphonates do not contain alkyl or alkenyl groups having more than about 6 carbon atoms.

Polyfunctionally substituted aromatic chelating agents are also useful in the compositions herein. See US patent 3,812,044, filed May 21, 1974 for Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene. A preferred biodegradable chelator for use herein is ethylene diamine disuccinate ("EDDS"), especially the [S, S] isomer, as described in US Pat. No. 4,704,233, November 3, 1987, to Hartman and Perkins. The compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelating agent or as a useful co-builder with, for example, insoluble builders such as zeolites, layered silicates and the like. . If used, the chelating agents will generally comprise from about 0.001% to about 15% by weight of the detergent compositions herein. More preferably, if used, the chelating agents will comprise from about 0.001% to about 3.0% by weight of such compositions.

FOAM SUPPRESSORS Compounds for reducing or suppressing the formation of foams can be incorporated into the compositions of the present invention when they are required by the proposed use, especially washing laundry in electrical washing devices. Other compositions, such as those designed for hand washing, may desirably be highly foaming and such ingredients may be omitted. The suppression of foaming may be of particular importance in what is referred to as the "high concentration cleaning process", as described in US 4,489,455 and 4,489,574 and in front-loading, European-style washing machines. A wide variety of materials can be used as foamed suppressors and are well known in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, third edition, volume 7, pages 430-447 (Wiley, 1979). The compositions herein will generally comprise from 0% to about 10% foaming suppressant. When used as foaming suppressors, the monocarboxylic fatty acids and salts thereof will typically be present in amounts of up to about 5%, preferably 0.5% -3% by weight of the detergent composition, although larger amounts may be used. Preferably, from about 0.01% to about 1% silicone foam suppressant is used, more preferably from about 0.25% to about 0.5%. These weight percentage values include any silica that can be used in combination with polyorganosiloxane, as well as any foaming suppressive adjuvant material that can be used. Monostearate phosphate buffer suppressors are generally used in amounts ranging from about 0.1% to about 2% by weight of the composition. The hydrocarbon foaming suppressors are typically used in amounts ranging from about 0.01% to about 5.0%, although higher levels may be used. Alcohol foaming suppressors are typically used at 0.2% -3% by weight of the finished compositions.

ALCOXYLATED POLYCARBOXYLATE Alkoxylated polycarboxylates such as those prepared from polyacrylates are useful herein to provide additional fat removal performance. Such materials are described in WO 91/08281 and PCT 90/01815 in p. 4 and following, incorporated herein by reference. Chemically, these materials comprise polyacrylates that have an ethoxy side chain for every 7-8 acrylic units. The side chains are of the formula - (CH2CH2O) m (CH2) nCH3 where m is 2-3 and n is 6-12. The side chains are attached by ester to a polyacrylate "backbone" to provide a "comb" type polymer structure. The molecular weight may vary, but typically it is in the range of about 2000 to about 50,000. Such alkoxylated polycarboxylates may comprise from about 0.05% to about 10% by weight of the compositions herein.

FABRIC SOFTENERS Various fabric softeners can optionally be used through washing, especially the impalpable smectite clays of the US Pat. No. 4,062,647, Storm and Nirschl, filed on December 13, 1977, as well as other softening clays known in the art, typically at levels of about 0.5% to about 10% by weight in the present compositions to provide the softener benefits of fabrics simultaneously with the cleaning of fabrics. Clay softeners • 10 can be used in combination with amino and cationic softeners as described, for example, in US Patent 4,375,416, Crisp, et al, March 1, 1983 and US Patent 4,291, 071, Harris et al, filed September 22, 1981. In addition, in the methods of laundry cleaning in the present, known fabric softeners include biodegradable types and can be used in pretreatment, main washing, after washing and in the aggregate drying mode. • PERFUMES Perfumes and perfumery ingredients useful in the present compositions and processes comprise a wide variety of natural and synthetic chemical ingredients including, but not limited to aldehydes, ketones, esters and the like. Also included are several natural and essential extracts which may comprise complex mixtures of ingredients such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar and similar. The finished perfumes typically comprise from about 0.01% to about 2% by weight of the detergent compositions herein, and the individual perfumery ingredients may comprise from about 0.0001% to about 90% of a finished perfume composition.

OTHER INGREDIENTS A wide variety of other ingredients useful in detergent compositions, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, may be included in the compositions herein. , etc. If high foaming is desired, foam reinforcements such as C10-C16 alkanolamides can be incorporated into the compositions, typically at levels of 1% -10%. C10-C14 monoethanol and diethanolamides illustrate a typical class of such foamed reinforcements. The use of such foamed reinforcements with adjuvant surfactants with high foaming such as amine oxides, betaines and sultaines indicated above is also advantageous. If desired, water-soluble magnesium and / or calcium salts such as MgCl 2, MgSO 2, CaCl 2, CaSO and the like can be added at typically 0.1% -2% levels, to provide additional foaming and to improve operation for removal of grease, especially for liquid dishwasher purposes. The various detersive ingredients used in the present compositions optionally can be further stabilized by absorbing the ingredients in a porous hydrophobic substrate., and then coating the substrate with a hydrophobic coating. Preferably, the detersive ingredient is mixed with a surfactant before being absorbed into the porous substrate. When used, the detersive ingredient is released from the substrate in the aqueous wash liquor, where it performs its proposed detersive function. The liquid detergent compositions may contain water and other solvents as carriers. Suitable primary or secondary alcohols of low molecular weight are exemplified by methanol, ethanol, propanol and isopropanol. Monohydric alcohols are preferred to solubilize surfactants, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (for example 1,3-propanediol, ethylene glycol, glycerin and 1) can also be used. 2-propanediol). The compositions may contain from 5% to 90%, typically 10% to 50% of such carriers. The detergent compositions herein will preferably be formulated so that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 11, preferably between about 7.0 and 10.5, and more preferably between about 7.0 and approximately 9.5. Liquid product formulations for dishwashing preferably have a pH between about 6.8 and about 9.0. Laundry products typically have a pH of 9-11. Techniques for controlling pH at recommended levels of use include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.

FORM OF COMPOSITIONS The compositions according to the invention can take various physical forms including granular, gel, tablet, stick and liquid form. The compositions include what are termed concentrated granular detergent compositions adapted to be added to a washing machine by means of a supply device placed in the drum of the machine with the dirty fabric load. The average particle size of the components of granular compositions according to the invention should preferably be such that no more than 5% of particles are greater than 1.7 mm in diameter and no more than 5% of the particles are less than 0.15 mm in diameter. diameter. The term "average particle size", as defined herein, is calculated by sieving a sample of the composition into several fractions (typically five fractions) of a series of Tyler sieves. The fractions by weight obtained in this way are plotted against the opening size of the screens. The average particle size is taken as the aperture size through which 50% by weight of the sample can pass. Certain preferred granular detergent compositions according to the present invention are of the high density type, now common in the market; these typically have a bulk density of at least 600 g / liter, more preferably from 650 g / liter to 1200 g / liter.

AGGLOMERATED TENSITIVE PARTICLES One of the preferred methods of supplying surfactants in consumer products is to make agglomerated particles of surfactant, which can take the form of flakes, nuggets, spheres, filaments, tapes, but preferably take the form of granules. A preferred way to process the particles is by agglomeration powders (for example aluminosilicate, carbonate) with high surface active pastes and to control the particle size of the resulting agglomerates within the specified limits. Such a process involves mixing an effective amount of powder with a high surfactant paste in one or more agglomerators such as a container agglomerator, a blade mixer Z or more preferably in an in-line mixer such as those manufactured by Schugi (The Netherlands) BV, 29 Chroomstraat 8211 AS, Lelystad, The Netherlands and Gebruder Lódige Maschinenbau GmbH, D-4790 Paderbom 1, Elsenerstrasse 7-9, Postfach 2050, Germany. More preferably, a high cut mixer is used, such as a CB Lódige (trademark). An elevated surfactant paste comprises from 50 wt% to 95 wt%, preferably 70 wt% to 85 wt% of surfactant typically used. The paste can be pumped into an agglomerator at a temperature high enough to maintain a moldable viscosity, but low enough to avoid degradation of the anionic surfactants used. A pulp operating temperature of 50 ° C to 80 ° C is typical.

WASHING METHOD IN LAUNDRY The washing machine methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or supplied therein an effective amount of a detergent composition in a laundry machine, in accordance with the invention. By an effective amount of the detergent composition it is meant here from 40 g to 300 g of product dissolved or dispersed in a washing solution in a volume of 5 to 65 liters, as are typical product dosages and volumes of washing solution commonly used in laundry methods of conventional machines.

As indicated, the surfactants are used herein in detergent compositions, preferably in combination with other detersive surfactants, at levels which are effective to obtain at least directional improvement in cleaning ability. In the context of a fabric laundry composition, such "levels of use" can vary widely, depending not only on the type and severity of the dirt and stains, but also on the temperature of the wash water, the volume of wash water and the type of washing machine. In a preferred use aspect, a delivery device is used in the washing method. The delivery device is charged with the detergent product, and is used to introduce the product directly into the drum of the washing machine before the start of the washing cycle. Its capacity in volume must be such that it is capable of containing sufficient detergent product which will normally be used in the washing method. Once the washing machine has been loaded with the garments, the dispensing device containing the detergent product is placed inside the drum. At the start of the wash cycle of the washing machine, water is introduced into the drum and the drum rotates periodically. The design of the delivery device can be such as to allow the containment of the dry detergent product but allow the release of this product during the wash cycle in response to its agitation as the drum rotates and also as a result of its contact with the water of the drum. washed. Alternatively, the delivery device may be a flexible package, such as a bag or sack. The bag may be of fibrous construction coated with a waterproof protective material so that it retains the content as described in the patent application.

European Published No. 0018678. Alternatively, it can be formed of a water-insoluble synthetic polymeric material that is provided with a seal at the edge or a closure designed to break in an aqueous medium, as described in the applications for European patents published Nos. 0011500, 0011501, 0011502 and 0011968. A convenient form of closure that can be opened in water comprises a water soluble adhesive placed along and sealing an edge of the bag formed of a waterproof polymeric film such as polyethylene or Polypropylene.

EXAMPLES In the following examples, the different abbreviations for the different ingredients used for the compositions have the following meanings.

MLAS Sodium alkylbenzene sulfonate with interrupted crystallinity LAS Sodium straight alkylbenzene sulfonate MBASx Primary branched middle chain alkyl (total carbon atoms = x) MBAExSz Alkyl sodium salt (total carbon number = z) ethoxylate (average EO = x) primary sulfate medium chain branched MBAEx Alkyl (average total carbons = x) ethoxylated (average EO = 8) ramified primary medium chain C18, 1, 4Disulfate 2-octadecyl butane 1,4-disulphate Endolase Enzyme endoglossase activity 3000 CEVU / g, sold by NOVO Industries A / S MEA Monoethanolamine DEA Dietalonamine PG Propanodioi EtOH Ethanol NaOH Solution of sodium hydroxide NaTS Toluenesulfonate sodium Citric acid Citric acid anhydrous CxyFA Fatty acid C1X-C1y CxyEz A primary alcohol branched C1x-1y condensed with an average of z moles of ethylene oxide Carbonate Anhydrous sodium carbonate with a particle size between 200 μm and 900 μm Citrate Trisodium citrate dihydrate activity 86.4% with a particle size distribution between 425 μm and 850 μm TFAA C16-18 alkyl N-methyl glucamide LMFAA C12-14 alkyl N-methyl glucamide APA C18-10 amido propyl dimethylamine Fatty acid (C12 / 14) C12-C14 fatty acid Fatty acid (TPK) Palm kernel fatty acid s Fatty acid (RPS) Rapeseed oil fatty acid Borax Na tetrahydrate decahydrate PAA Polyacrylic acid (pm = 4500) PEG Polyethylene glycol (MW = 4600) MES Alkyl methyl ester sulfonate SAS Sulphate secondary alkyl NaPS Paraffin sodium sulfonate CxyAS C1x-C1 and sodium alkyl sulfate specific) CxyEzS C1x-C1 and sodium alkyl sulfate condensed with z moles of oxide ethylene (or other salt, if specified) CxyEz A branched primary alcohol of C1x-1 and condensed with an average of z moles of ethylene oxide QAS R2.N + (CH3) x ((C2H40) and H) z with R2 = C8- C18 x + z = 3, x = 0 to 3, z = 0 to 3, y = 1 to 15. STPP Anhydrous sodium tripolyphosphate Zeolite A Alumino hydrous sodium silicate of formula Na12 (A102SiO2) 12.27H2O having a primary particle size in the range of 0.1 to 10 micrometers NaSKS-6 Crystalline layered silicate of formula d- Na2Si205 Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400 μm and 1200 μm Silicato amorphous sodium silicate (Si02: Na20, ratio 2.0) Sodium Sulphate Sulphate anhydrous PAE Tetraethylene ethoxylated pentamine PIE Ethoxylated polyethyleneimine PAEC Methylated quaternized ethoxylated methyldihexylenetriamine MA / AA Maleic / acrylic acid copolymer 1: 4, average molecular weight of approximately 70,000 CMC Sodium carboxymethylcellulose Protease Protective activity enzyme 4KNPU / g sold by NOVO Industries A / S under the trade name Savinase Celulasa Activity cellulite enzyme 1000 CEVU / g sold by NOVO Industries A / S under the trade name ial Carezyme Amylase Activity amylolytic enzyme 60 KNU / g sold by NOVO Industries A / S under the trade name Termamyl 60T Lipase Lipolytic activity enzyme 100kLU / g sold by NOVO Industries A / S under the trade name Lipolase 0 PB1 Sodium perborate bleach Monohydrate PB4 Sodium perborate bleach tetrahydrate Percabonate Sodium carbonate with nominal formula 2Na2C03.3H202 NaDCC Sodium dichloroisocyanurate NOBS Sodium salt of nonanoyloxybenzenesulfonate 5 TAED Tetraacetylethylenediamine DTPMP Diethylenetriamine penta (methylene phosphonate) sold by Monsanto as Dequest 2060 Phthalocyanine sulfonated zinc whitener bleach encapsulated in soluble polymer of dextrin or Brightener 1 4,4'-bis (2-sulfoesteryl) biphenyl disodium Brightener 2 4,4'-bis (4-anilino-6-morpholino-1, 3,5-triazin-2-yl) amino) stilbene-2, Disodium 2'-disulfonate HEDP 1, 1-hydroxyethane diphosphonic acid SRP 1 Esters capped at the end with sulfobenzoyl with oxyethylene and terephthaloyl oxyethylene backbones SRP 2 Ethoxylated sulfonated terephthalate polymer SRP 3 Ethoxylated terephthalate polymer topped with methyl Silicone antifoam Polydimethyl siloxane foam controller with siloxane-oxyalkylene copolymer as a dispersing agent with a ratio of foam controller to dispersing agent 10: 1 to 100: 1 Isofol 16 Trademark Condea for Guerbet C16 alcohols (average) CaCl2 Calcium Chloride MgCl2 Magnesium Chloride Diamine Alkyldiamine, for example 1,3-propanediamine, Dytek EP, Dytek A, where Dytek is a trademark of Dupont, 2-hydroxypropane diamine DTPA Diethylene triamine pentaacetic acid Dimethicone Combination in weight ratio 40 (gum) / 60 (fluid) dimethicone rubber SE-76 from General Electric Division Silicones, and a dimethicone fluid that has a viscosity of 350 centistokes NTA Nitrate Nitrilotriacetate BPP Butoxy propoxy propanol EGME Ethylene glycol monohexyl ether PEG DME Dimethyl polyethylene glycol, mwt 2000 PVP K60 Vinylpyrrolidone homopolymer, av mwt 160,000 Minor Low level materials such as dyes, perfumes, or dyes and / or fillers (eg talcum, NaCl, sulphate) .

Unless stated otherwise, the ingredients are anhydrous. In the following examples, all levels are indicated as% by weight of the composition. The following examples are illustrative of the present invention but do not mean that they are limited or that they define their scope in some other way. All parts, percentages and proportions used herein are expressed as weight percent unless otherwise specified.

EXAMPLE 6 The following laundry detergent compositions A to D, suitable for hand washing of soiled fabrics, are prepared according to the invention: EXAMPLE 7 The following laundry detergent compositions E to H, suitable for hand washing of soiled fabrics, is prepared according to the invention: EXAMPLE 8 The following laundry detergent compositions I to L suitable for hand washing of soiled fabrics, are prepared according to the invention: EXAMPLE 9 The following laundry detergent compositions A to E are prepared according to the invention: EXAMPLE 10 The following laundry detergent compositions F to K are prepared according to the invention: EXAMPLE 11 The following liquid laundry detergent compositions L a P are prepared according to the invention: EXAMPLE 12 A non-limiting example of a non-aqueous liquid detergent containing laundry bleach is prepared, and has the following composition: The resulting composition is an anhydrous and stable heavy-duty liquid laundry detergent for laundry, which provides excellent performance for removal of stains and grime, when used in normal fabric laundry operations.

EXAMPLE 13 The following examples further illustrate the invention herein with respect to the manual dishwashing liquid.

EXAMPLE 14 The following examples further illustrate the invention herein with respect to shampoo formulations.

EXAMPLE 15 Various stick compositions having a composition can be made.

EXAMPLE 16 The following laundry detergent compositions GG to KK repair according to the invention: EXAMPLE 17 The following high density detergent formulations LL to 00 are prepared according to the present invention: EXAMPLE 18 The following are examples of hard surface cleaners • 15

Claims (10)

NOVELTY OF THE INVENTION CLAIMS

1. A cleaning composition, comprising: a) 0.1% to 99.9% by weight of the composition of an alkylarylsulfonate surfactant system comprising from 10% to 100% by weight of the surfactant system of two or more alkylarylsulfonate surfactants of interrupted crystallinity, formula: wherein D is SO3", M is a cation or a mixture of cations, q is the valence of the cation, a and b are numbers that are selected so that the composition is electroneutral, Ar is selected from benzene, toluene and combinations thereof and B comprises the sum of at least one primary hydrocarbyl portion containing from 5 to 20 carbon atoms and one or more portions of interrupted crystallinity, wherein the interrupted crystallinity portions interrupt or branch off the hydrocarbyl portion; the alkylarylsulfonate surfactant system has an interruption in crystallinity to the extent that the temperature of critical solubility of sodium, as measured by the CST test, is no greater than 40 ° C, and wherein the surfactant alkylsulfonate system has at least less one of the following properties: the percentage of biodegradation, measured by the modified SCAS test, which exceeds that of tetrapropylenebenzene sulfonate; n in weight of non-quaternary carbon atoms with respect to quaternaries in B of at least 5: 1; and b) from 0.00001% to 99.9% by weight of the composition of the adjuvant ingredients of the cleaning composition, at least one of which is selected from the group consisting of: i) detersive enzymes; ii) organic detergent improvers; iii) oxygen bleaching agent; iv) bleach activators; v) transition metal bleach catalysts; vi) oxygen transfer agents and precursors; vii) polymeric soil release agents; viii) water-soluble ethoxylated amines that have clay grime removal and anti-redeposition properties; ix) polymeric dispersing agents; x) polymeric agents to inhibit dye transfer; xi) alkoxylated polycarboxylates; and xii) mixtures thereof.

2. The cleaning composition according to claim 1, wherein Ar is benzene.

3. The cleaning composition according to any of claims 1-2, wherein the alkylarylsulfonate surfactants of interrupted crystallinity include at least two isomers that are selected from: i) ortho-, meta- and para-based isomers the binding positions of the substituents with respect to Ar, when Ar is a substituted or unsubstituted benzene; ii) position isomers based on the binding positions of the substituents with respect to B; and iii) stereoisomers based on chiral carbon atoms in B. The compositions according to any of claims 1-3, wherein the alkylarylsulfonate surfactant system further comprises from 0% to 85% by weight of the surfactant system of one or more alkylarylsulfonate surfactants without interrupted crystallinity of formula: wherein D, M, q, a, b, Ar are as defined for the alkylarylsulfonate surfactants of interrupted crystallinity; and L is a linear hydrocarbyl portion containing from 5 to 20 carbon atoms. 5. The composition according to any of claims 1-4, wherein B includes odd and even carbon chain lengths. 6. The composition according to any of claims 1-5, wherein the primary portion of B is exactly a straight hydrocarbyl portion having from 7 to 16 carbon atoms and wherein the portion or portions that disrupt the crystallinity are select from: i) branches attached to B which are selected from C1-C3 alkyl, C1-C3 alkyloxy, hydroxy and mixtures thereof; I) portions which interrupt the structure of B, selected from ether, sulfone, silicone; and i) mixtures thereof. 7. The composition according to any of claims 1-6, wherein at least 60% by weight of the surfactant system of the alkylated crystallinity interrupter surfactant is in the form of isomers, wherein Ar binds to B at the second or third carbon atom in the linear hydrocarbyl portion thereof. The cleaning composition according to any of claims 1-7, wherein the alkylarylsulfonate surfactant system has an interruption in crystallinity to the extent that the temperature of critical sodium solubility, measured by the CST test, is not greater than 20 ° C. 9. The cleaning composition according to any of claims 1-8, wherein the alkylarylsulfonate surfactant system has an interruption of crystallinity to the extent that the temperature of critical calcium solubility, measured by the CST test, is not greater than 80 ° C. 10. The cleaning composition according to any of claims 1-9, wherein the percentage of biodegradation, as measured by the modified SCAS test, is at least 60%.