MXPA00000138A - Non-aqueous detergent compositions containing bleach - Google Patents

Abstract

Non-aqueous liquid detergent compositions comprising a bleach precursor and/or bleaching agent further comprising a compound which is capable of interacting with the oxygen released by the decomposition of the bleach precursor and/or bleaching agent.

Description

COMPOSITIONS NON-AQUEOUS DETERGENTS CONTAINING WHITENER FIELD OF THE INVENTION The present invention relates to non-aqueous detergent compositions containing a source of bleach.

BACKGROUND OF THE INVENTION Detergent products in liquid form are commonly considered more convenient to use than detergent products in dry or particulate powder. Therefore, said detergents have found a substantial acceptance of the consumers. Said detergent products can be easily measured, they dissolve rapidly in the wash water, they are capable of being easily applied in concentrated solutions or dispersions to soiled areas on garments that will be washed and do not form dust. They also normally occupy less storage space than granulated products. In addition, said detergents may have incorporated in their formulations materials that could not support drying operations without deterioration, operations that are commonly used in the manufacture of detergent products in particles or granulates.

Although said detergents have several advantages over granular detergent products, they also inherently possess several disadvantages. In particular, the components of the detergent composition which may be compatible with each other in granulated products may tend to interact or react with one another. In this way, components such as enzymes, surfactants, perfumes, brighteners, solvents and especially bleach and bleach activators can be especially difficult to incorporate into liquid detergent products which then have a degree of acceptable chemical stability. One approach to improving the chemical compatibility of detergent composition components in detergent products has been to formulate non-aqueous (or anhydrous) detergent compositions. In such non-aqueous products, at least some of the normally solid detergent composition components tend to remain insoluble in the liquid product and are therefore less reactive with each other than if they had been dissolved in the liquid matrix. Non-aqueous liquid detergent compositions, including those containing reactive materials such as peroxygen bleaching agents, have been described, for example, in Hepworth et al., U.S. Pat. 4,615,820, issued October 17, 1986; Schuitz et al., Patent of E.U.A. 4,929,380, issued May 29, 1990; Schuitz et al., Patent of E.U.A. do not. 5,008,031, issued on April 16, 1991; Eider et al., EP-A-030,096, published June 10, 1981; Hall et al., WO 92/09678, published June 11, 1992 and Sanderson et al., EP-A-565,017, published October 13, 1993. A particular problem that has been observed with the incorporation of bleach precursors. In non-aqueous detergents, it includes the chemical stability of the bleach and the bleach precursor. Bleach and bleach precursors must remain chemically stable in the concentrate, while reacting rapidly with each other in the dilution of the wash liquor. Unfortunately, the bleach and / or bleach precursor present in the concentrate show some degree of decomposition. The above is usually accompanied by the evolution of oxygen, thus creating an internal pressure in the container that accumulates over time. Especially in plastic containers, the containers are progressively subjected to deformation due to the accumulation of internal pressure. This phenomenon is frequently referred to as "bulging". This phenomenon is especially acute in warm countries where containers can be exposed particularly at high temperatures. In some cases, the bulge may also be severe to induce a base deformation such that the container can no longer be held in the straight position. For example, in supermarkets, containers can fall off shelves. The bulging problem can be resolved to some extent by the ventilation systems. However, ventilation systems are he has. .. «. Jtfaafe. expensive to be incorporated into the packaging design, and tend to fail when in contact with the liquid product (for example, tended or overturned bottles), or may cause the product to leak. Therefore, there is a continuing need to reduce the amount of packing bulge for non-aqueous liquid detergents containing bleach. It has now been discovered that bulking can be reduced by specific compounds that are capable of interacting with the oxygen developed by non-aqueous liquid detergents.

BRIEF DESCRIPTION OF THE INVENTION According to the present invention, non-aqueous liquid detergent compositions containing specific compounds capable of interacting with oxygen are provided.

DETAILED DESCRIPTION OF THE INVENTION In accordance with the present invention, it has been discovered that the problem of bulging of the package is reduced by the addition of specific compounds in the non-aqueous liquid detergent compositions which serve to interact with the oxygen released by the decomposition of the source of bleach. "Interaction" means that said compounds react or that oxygen is absorbed by said compound. As a consequence, said specific compounds are effective in reducing or eliminating the oxygen that could accumulate in the package. Preferred compounds that are capable of reacting with oxygen are oxygen scavengers. Preferred oxygen scavengers are compounds that contain a metal ion. Examples are iron, cobalt and manganese. According to a preferred embodiment, the compound is a catalyst that contains metal ion. Preferred catalysts are bleach catalysts which are transition metal complexes and a rigid macropolyclic ligand. The phrase "macropolycyclic rigid ligand" is sometimes abbreviated as "MRL" in the following description. The amount used is a catalytically effective amount of about 1 ppb or more, for example up to about 99.9%, more typically about 0.001 ppm or more, preferably about 0.05 ppm about 500 ppm (where "ppb" denotes parts per billion by weight and "ppm" denotes parts per million by weight, suitable transition metals, for example, Mn, are illustrated below. "Macropolyclics" refers to an MRL that is macrocycle and polycyclic. "Polycyclic" refers to being less bicyclic.The term "rigid", as used herein, includes "having a superstructure" and "cross-bridge shape." "Rigid has been defined as the limited conversion of flexibility. : see DH Busch., Chemical Reviews., (1993), 93, 847-860, incorporated by reference, more particularly, "rigid", as used herein, refers to the fact that the MRL must be definitely more rigid than a macrocycle ("macrocycle orig inal ") that is otherwise identical (having the same size and type of ring and number of atoms in the main ring) but lacks a superstructure (especially link portions or, preferably cross bridge portions) found in the MRLs. To determine the comparative stiffness of macrocycles with and without superstructures, the practitioner must use the free form (not the metal-bonded form) of the macrocycles. Rigidity is well known to be useful in comparison macrocycles; suitable tools to determine, measure and compare stiffness including computational methods (see, for example, Zimmer, Chemical Reviews, (1995), 95 (38), 2629-2648 or Hancock et al., Inorganic Chimica Acta, (1989) , 164, 73-84). A determination that if a macrocycle is more rigid than another can often be done by simply making a molecular model, in this way, it is usually not essential to know the configurational energies in absolute terms or to compute them accurately. The excellent comparative determinations of stiffness of one macrocycle versus another can be made using computational tools based on inexpensive personal computers, such as ALCHEMY III, commercially available from Tripos Associates. Tripos also has more expensive software available that allows not only comparative but absolute determinations; alternatively, SHAPES can be used (see Zimmer cited above). One observation that is significant in the context of the present invention is that there is an optimum part for the present purposes when the original macrocycle is distinctly flexible when compared to the cross-bridge shape. In this way, unexpectedly, it is preferred to use the original macrocycles containing at least four donor atoms, such as cyclan derivatives, and to join them by cross-bridge, instead of starting with a more rigid original macrocycle. Another observation is that cross-bridge macrocycles are significantly preferred over macrocycles that are bridged in another way. Preferred MRLs herein are a special type of ultra-rigid ligand that is cross-linked. A "cross bridge" is illustrated in a non-limiting manner in 1.11 below. In 1.11 the crossed bridge is a portion -CH2CH2-. The above forms a bridge N1 and N8 in the illustrative structure. In comparison, a "same-side" bridge, for example, if a bridge is to be introduced in N1 and N12, it would not be sufficient to constitute a "cross bridge" and consequently it would not be preferred. Suitable metals in rigid ligand complexes include Mn (ll), Mn (lll), Mn (IV), Mn (V), Fe (ll), Fe (lll) Fe (IV), Co (l), Co (ll), Co (lll), Ni (l), Ni (ll), Ni (lll), Cu (l), Cu (ll), Cu (lll), Cr (ll), Cr (lll), Cr (IV), Cr (V), Cr (VI), V (lll), V (IV), V (V), Mo (IV), MO (V), Mo (VI), W (V), W (VI), Pd (ll), Ru (ll), j ^ jfe Ru (lll), and Ru (IV). Preferred transition metals in the bleach catalyst and instant transition metal include manganese, iron, and chromium. Preferred oxidation states include the oxidation states (II) and (III). Manganese (II) is included in the low spin configuration and high spin complexes. It should be noted that complexes such as low spin Mn (ll) complexes are rare throughout the coordination chemistry. The designation (II) or (III) denotes a coordinated transition metal having the necessary oxidation state; the coordinate metal atom is not a free ion or one that has only water as a ligand. In general, as used herein, a "ligand" is any portion capable of linking the direct covalent to a metal ion. The ligands may be charged or neutral and may vary widely, including simple monovalent donors, such as chlorine, or simple amines that form a single coordinate bond and a single point of attachment to a metal; to oxygen or ethylene, which can form a three-membered ring with a metal and thus can be said to have two potential points of attachment, to larger portions such as ethylenediamine or aza macrocycles, which form up to the maximum number of single bonds to one or more metals that provide the available sites in the metal and the number of isolated pairs or alternating free ligand binding sites. The numerous ligands can form different bonds to the single donor bonds, and can have multiple binding sites.

The ligands useful herein can be included in several groups: the MRL, preferably a cross-bridge macropolicicy (preferably there will be only one MRL in a useful transition metal complex, but also, for example two, may be present, but not in preferred mononuclear transition metal complexes); in addition, optional ligands, which in general are different from the MRL (generally there will be from 0 to 4, preferably from 1 to 3 of said ligands); and ligands transiently associated with the metal as part of the catalytic cycle, the latter typically being related to water, hydroxide, oxygen or peroxide. The ligands of the third group are not essential to define the metal bleach catalyst, which is a stable, isolable chemical compound that can be fully characterized. Ligands that bind to metals through donor atoms each have at least a single electron isolated pair available for donation or a metal having a donor capacity, or potential denticity, at least equal to the number of donor atoms. . In general, the donor capacity can be exercised totally or partially. Generally, the MRLs herein may be viewed as a result of the imposition of additional structural rigidity on the specifically selected "original macrocycles". More generally, the MRLs (and the corresponding transition metal catalysts) herein properly comprise: (a) at least one macrocycle main ring comprising four or more heteroatoms; and (b) a covalently connected metal-superstructure capable of increasing the stiffness of the macrocycle, preferably selected from: (i) a bridge superstructure, such as a link portion; (I) a cross bridge superstructure, such as a cross bridge link portion; and (iii) combinations thereof. The term "superstructure" is used herein as defined in the literature by Busch and others, see, for example, Busch articles in "Chemical Reviews". The preferred superstructures herein not only drive the stiffness of the original macrocycle, but also favor the bending of the macrocycle so that it coordinates a metal in a groove. Suitable superstructures can be remarkably simple, for example, a link portion such as any of those illustrated in 1.9 and 1.10 below can be used.

\ (CH2) n where n is an integer, for example 2 to 8, preferably less than 6, typically 2 or 4, or 1. 10 wherein m and n are integers of about 1 to 8, more preferably 1 to 3; Z is N or CH; and T is a compatible substituent, for example H, alkyl, trialkylammonium, halogen, nitro, sulfonate, or the like. The aromatic ring in 1.10 can be replaced by a saturated ring, in w the Z atom that connects to the ring can contain N, O, S or C. Without pretending to be limited by theory, it is believed that the preorganization constructed in the MRLs in the present that leads to extra kinetics and / or thermodynamic stability of their metal complexes arise from one or both of the topological constraints and driven stiffness (loss of flexibility) compared to the original free macrocycle that has no superstructure. The MRLs, as defined herein, and their preferred cross-bridge subfamily, w may be "ultra-rigid", combine two sources of fixed pre-organization. In the preferred MRLs herein, the original macrocycle linking portions and rings combine to form ligands that have a significant "fold" extension, typically greater than several known superstructured ligands in w a Ü ^ j ^ É | superstructure joins a highly flat macrocycle, often unsaturated. See, for example: D. H. Busch, Chemical Reviews, (1993), 93, 847-880. In addition, MRLs in the present have a number of particular properties, including: (1) they are characterized by very high proton affinities, as in so-called "proton sponges"; (2) tend to react slowly with multivalent transition metals, w, when combined with (1) above, the synthesis of their complexes with certain difficult hydrolysable metal ions in hydroxylic solvents; (3) when coordinated with transition metal atoms as identified above, MRLs result in complexes that have exceptional kinetic stability, so that metal ions only disassociate extremely slowly under conditions that can destroy complexes with ordinary ligands; and (4) said complexes have exceptional thermodynamic stability; however, the unusual kinetics of the MRL dissociation of the transition metal can affect the conventional equilibrium measurements that can quantify said property. In one aspect of the present invention, MRLs include those comprising: (i) an organic macrocycle ring containing 4 or more donor atoms (preferably at least 3, more preferably at least 4, of said donor atoms are N) ) separated from each other by covalent bonds of at least 1, preferably 2 or 3, non-donor atoms, 2 to 5 (preferably 3 to 4, more preferably 4) of said donor atoms w coordinate with the same transition metal in the complex; and (ii) a linker portion, preferably a cross-bridge chain, w covalently connects at least 2 (preferably non-adjacent) donors of the organic macrocycle ring, said donor atoms covalently connected (preferably not adjacent) being bridgehead donor atoms that coordinate with the same transition metal in the complex, and wherein said link portion (preferably a cross bridge chain) comprises from 2 to about 10 atoms (preferably the bridge chain) crossed is selected from 2, 3 or 4 non-donor atoms, and 4-6 non-donor atoms with another donor atom). Suitable MRLs are further illustrated in a non-limiting manner by the following compound: 1. 1 1 This is an MRL according to the invention, w is a highly preferred, cross-bridge cyclam derivative, substituted with methyl (all tertiary nitrogen atoms). Formally, said ligand is called 5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane using the extended von Baeyer system. See "A Guide to IUPAC Nomenclature of Organic Compounds: Recommendations 1993", R. Panic, W. H. Powell and J-C Richer (Eds.), Blackwell Scientific Publications, Boston, 1993; see especially section R-2.4.2.1. According to conventional terminology, N1 and N8 are "bridgehead atoms"; as defined herein, more particularly "bridgehead donor atoms" since they have isolated pairs capable of donation to a metal. N1 which is connected to two donor atoms without a bridge head, N5 and N12, by distinct saturated carbon chains 2,3,4 and 14,13 and to the bridgehead donor atom N8 by means of a "binding portion" a, b which is a carbon chain saturated in the present of 2 carbon atoms. N8 is connected to two donor atoms without bridge heads, N5 and N12, by different chains 6, 7 and 9, 10, 11. The string a, b is a "link portion" as defined herein, and is the preferred special type, referred to as the "cross-bridge" portion. The "macrocyclic ring" of the anterior ligand, or "major ring" (IUPAC), includes the 4 donor and chain atoms 2,3,4; 6.7; 9,10,11 and 13,14 but not a, b. Said ligand is conventionally bicyclic. The short bridge or "link portion" a, b is a "cross bridge" as defined herein, with a, b bisecting the macrocyclic ring. The MRLs herein are obviously not limited to being synthesized from any preformed macrocycle plus the preformed "stiffening" or "conformational modifier" element: on the contrary, a wide variety of synthetic media, such as template synthesis, are useful. . See for example Busch et al, reviewed in "Heterocyclic compounds: Aza-crown macrocycles ", JS Bradshaw et al. Transition metal bleach catalysts useful in the compositions of the invention may generally include known compounds wherein they conform to the definition herein, as well as, more preferably, any of the large number of novel compounds expressly designed for current laundry or cleaning uses, and illustrated in a non-limiting manner by any of the following: Dichloro-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2 ] hexadecane-manganese (II) Dichloro-4,10-dimethyl-1, 4,7,10-tetraazabicyclo [5.5.2] tetradecane-manganese (II) Diaxa-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II) Hexafluorophosphate, aqueous-hydroxy-5,12-dimethyl-1, 5,8,12- hexafluorophosphate tetraazabicyclo [6.6.2] hexadecane-manganese (lll) Diacuo-4,10-dimemethyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane-manganese (II) diakano-5 tetrafluoroborate, 12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II) Diacuo-4,10-dimethyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane-tetrafluoroborate manganese (II) Dichloro-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese hexafluorophosphate (III) «^ N * - - • - *" * - Dichloro-5,12-di-n-butyl-1, 5,8,12-tetraaza-bicyclo [6.6.2] hexadecane-manganese (II); 5,12-dibenzyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II); Dichloro-5-n-butyl-12-methyl-1, 5,8,12-tetraaza-bicyclo [6.6.2] hexadecane-manganese (ll); Dichloro-5-n-octyl-12-methyl-1, 5,8,12-tetraaza-bicyclo [6.6.2] hexadecane-manganese (II); Dichloro-5 -n-butyl-12-methyl-1, 5,8,12-tetraaza-bicyclo [6.6.2] hexadecane-manganese (II); Dichloro-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [ 6.6.2] hexadecane-iron (ll); Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane-iron (II); Dichloro-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-copper (ll); Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane-copper (II); Dichloro-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-cobalt (ll); Dichloro-4,10-dimethyl-1, 4,7,10-tetraazabicyclo [5.5.2] tetradecane-cobalt (II); Dichloro-5,12-dimethyl-4-phenyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II); Dichloro-4,10-dimethyl-3-phenyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane-manganese (II); Dichloro-5,12-dimethyl-4,9-diphenyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II); Dichloro-4,10-dimethyl-3,8-diphenyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane-manganese (II); Dichloro-5,12-dimethyl-2, 11-diphenyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II); Dichloro-4,10-dimethyl-4,9-diphenyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane-manganese (II); Dichloro-2,4,5,9,11,16-hexamethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II); Dichloro-2,3,5,9,10,12-hexamethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II); Dichloro-2,2,4,5,9,9,11,18-octamethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II); Dichloro-2,2,4,5,9,11,11,18-octamethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II); Dichloro-3,3,5,10,10,12-hexamethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II) Dichloro-3,5,10,12-tetramethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II) Dichloro-3-butyl-5, 10,12-trimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese ( ll) Dichloro-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II) Dichloro-1, 4,7,10-tetraazabicyclo [5.5.2] tetradecane-manganese (II) Dichloro-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-iron (II) Dichloro-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane-iron (II) Acuo-chloro-2- (2-hydroxyphenyl) ) -5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II) Acuo-chloro-10- (2-hydroxybenzyl) -4,10-dimethyl-1,4, 7,10-tetraazabicyclo [5.5.2] tetradecane-manganese (II) Chloro-2- (2-hydroxybenzyl) -5-methyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II) Chloro-10- (2-hydroxybenzyl) -4-methyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane-manganese (II) Chloro-5-methyl-12- (2-picolyl) -chloride 1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II) Chloro-4-methyl-10- (2-picolyl) -1,4,7,10-tetraazabicyclo [5.5.2] tetradecane -manganese (ll) Dichloro-5- (2-sulfate) dodecyl-12-methyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (lll) Acuo-chloro-5- (2-sulfate ) dodecyl-12-methyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II) Acuo-chloro-5- (3-sulfonopropyl) -12-methyl-1, 5,8,12 -tetraazabiciclo [6.6.2] hexadecane manganese (II) chloride dichloro-5- (trimethylammoniumpropyl) dodecyl-12-methyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (lll) Dichloro- 5,12-dimethyl-1, 4,7,10,13-pentaazabicyclo [8.5.2] heptadecane-manganese (II) Dichloro-14,20-dmethyl-1, 10,14,20-tetraazatricyclo [8.6. 6] docosa-3 (8), 4,6-triene-manganese (II) Dichloro-4,11-dimethyl-1, 4,7,11-tetraazabicyclo [6.5.2] pentadecane-manganese (II) Dichloro-5 , 12-dimethyl-1, 5,8,12-tetraazabicyclo [7.6.2] heptadecane manganese (II) Dichloro-5,13-dimethyl-1, 5,9,13-tetraazabicyclo [7.7.2] heptadecane manganese (II Dichlor o-3,10-bs (butylcarboxyl) -5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II) Diacuo-3,10-dicarboxy -5.12-dimethyl-1, 5,8,12- tetraazabicyclo [6.6.2] hexadecane manganese (II) hexafluorophosphate chloro-20-methyl-1, 9,20,24,25-pentaazatetracyclo [7.7.7.137 0.111 15] pentacosa-3,5,7 (24), 11, 13,15 (25) -hexaeno Manganese (II) trifluoromethanesulfonate trifluorometansulfono-20-methyl-1, 9,20,24,25- pentaazatetracyclo [7.7 .7.13'7.111'15] pentacosa-3,5,7 (24), 11, 1315 (25) -hexaeno- manganese (II) trifluoromethanesulfonate trifluorometansulfono-20-methyl-1, 9,20, 24,25- pentaaza -tetracycle [7.7.7.13'7.111'15.] pentacosa-3,5,7 (24), 11, 13,15 (25) - hexane-iron (II) Chloro-5,12,17-trimethyl-hexafluorophosphate 1, 5,8, 12,17- pentaazabicyclo [6.6.5] nonadecane manganese (II) hexafluorophosphate Chloro-4,10,15-trimethyl-1, 4,7,10,15- pentaazabicyclo [5.5.5] heptadecane Manganese (II) Chlorine-5,12,17-trimethyl-1, 5,8,12,17-pentaazabicyclo [6.6.5] nonadecane-manganese (II) chloride Chloro-4,10,15-trimethyl-1, 4,7, 10,15-pentaazabicyclo [5.5.5] heptadecane-manganese (II). The practitioner can also benefit if certain terms receive additional definition and illustration. As used herein, "macrocyclic rings" are covalently linked rings formed of 4 or more donor atoms (eg, heteroatoms such as a nitrogen or oxygen) with carbon chains connecting them, and any macrocycle ring as defined in the present it must contain a total of at least ten, preferably at least twelve, atoms in the macrocycle ring. An MRL herein may contain more than one ring of any kind per ligand, but at least one macrocycle ring must be identifiable. In addition, in the most preferred embodiments, neither of the two heteroatoms is directly connected. Preferred transition metal bleach catalysts are those wherein the MRL comprises an organic macrocycle ring (main ring) containing the least 10-20 atoms, preferably 12-18 atoms, more preferably from about 2 to about 20 atoms, more preferably 12 to 16 atoms. "Donor atoms" herein are heteroatoms such as nitrogen, oxygen, phosphorus or sulfur, which when incorporated into a ligand still have at least one isolated pair of electrons available to form a donor-acceptor bond with a metal. The preferred transition metal bleach catalysts are those wherein the donor atoms in the organic macrocycle ring of the cross-bridge MRL are | ^ ^^ ggdj ^ gjj are selected from the group consisting of N, O, S and P, preferably N and O, and most preferably all N. Cross-bridge MRLs comprising 4 or 5 atoms are also preferred. donors, which are coordinated with the same transition metal. The most preferred transition metal bleach catalysts are those wherein the cross-bridge MRL comprises 4 nitrogen donor atoms that coordinate with the same transition metal, and those where the cross-bridge MRL comprises 5 coordinated nitrogen atoms with the same transition metal. "Non-donor atoms" of the MRL herein are more commonly carbon, although a number of atom types may be included, especially in optional exocyclic substituents, (such as "pendant" portions, illustrated below) of the macrocycles, which they are not donor atoms for essential purposes to form metal catalysts, and they are not carbon either. Thus, in the broadest sense, the term "non-donor atoms" may refer to any atom essential to form donor bonds as a catalyst metal. Examples of such atoms may include heteroatoms such as sulfur as incorporated in a non-coordinating sulfonate group, phosphorus as incorporated in a phosphonium salt portion, phosphorus as incorporated in a P (V) oxide, a non-transition metal, or similar. In certain preferred embodiments, all non-donor atoms are carbon.

, The transition metal complexes of MRLs can be prepared in any convenient way. Two of these preparations are illustrated below: Synthesis of [Mn (Bciclam) CI 1 (a) Method I The "Bciclam" (5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane) was prepared by a synthesis method described by G.R. Weisman, et al., J.Amer.Chem.Soc., (1990), U2, 8604. The Bciclam (1.00 g., 3.93 mmol) was dissolved in CH3CN (35 mL, distilled from CaH2). The solution was then evacuated to 15 mm until the CH3CN began to boil. The flask was then brought to atmospheric pressure with Ar. Said degassing procedure was repeated 4 times. Mn (pyridine) 2 Cl 2 (1.12 g., 3.93 mmol), synthesized according to the literature procedure of H. T. Witteveen et al., J. lnorq. Nucí Chem., (1974), 36, 1535, was added under Ar. The hazy reaction solution began to darken slowly. After stirring overnight at room temperature, the reaction solution turned dark brown with fine suspended particles. The reaction solution was filtered with a 0.2μ filter. The filtrate was a light yellow color. Said filtrate was evaporated to dry using a rotoevaporator. After drying overnight at 0.05 mm at room temperature, 1.35 g was collected. of white solid product, 90% yield. Elemental Analvsis:% Mn. 14.45; % C. 44.22; % H. 7.95; theoretical for [Mn (Bciclam) CI2], MnC1 H30N4CI2, MW = 380.26. Found:% Mn, 14.98; % C, 44.48; % H, 7.86; Ion Spray Mass Spectroscopy shows a peak greater than 354 mu corresponding to [Mn (Bciclam) (format)] +. (b) Method II. The freshly distilled Bciclam (25.00 g, 0.0984 mole), which was prepared by the same method above, was dissolved in CH3CN (900 mL, distilled from CaH2). The solution was then evacuated to 15 mm until the CH3CN began to boil. The flask was then brought to atmospheric pressure with Ar. Said degassing procedure was repeated 4 times. MnCl2 (11.25 g, 0.0894 moles) was added under Ar. The hazy reaction solution darkened immediately. After stirring for 4 hours under reflux, the reaction solution turned dark brown with fine suspended particles. The reaction solution was filtered through a 0.2μ filter under dry conditions. The filtrate was light yellow. Said filtrate was evaporated to dry using a rotoevaporator. The resulting yellow solid was dried overnight at 0.05 mm at room temperature. He ^^ jjljj ^^ solid was suspended in toluene (100 mL) and heated to reflux. The toluene was decanted and the procedure was repeated with another 100 mL of toluene. The rest of the toluene was removed using a rotoevaporator. After drying overnight at .05 mm at room temperature, 31.75 g was collected. from a light blue solid product, at 93.5% yield, Elemental Analvsis:% Mn, 14.45; % C, 44.22; % H, 7.95:% N, 14.73; % CI, 18.65; theoretical for [Mn (Bciclam) CI2], MnC? 4H30N4CI2, MW = 380.26. Found:% Mn, 14.69; % C,% C, 44.69; % H, 7.99; % N, 14.78; % CI, 18.90 (Karl Fischer water, 0.68%). Ion spray mass spectroscopy showed a peak greater than 354 mu corresponding to [Mn (Bciclam) (format)] +.

Bleach source An essential component of the invention is a bleach precursor and / or a bleaching agent. Suitable bleach precursors for inclusion in the composition according to the invention typically contain one or more N- or O-acyl groups, precursors that can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, nitriles and acylated derivatives of imidazoles and oximes, and examples of useful materials within these classes are described in GB-A-1586789. Suitable esters are described in GB-A-836988, 864798, 147871, 2143231 and EP-A-0170386. Acrylation products of sorbitol, Glucose and all saccharides with benzoylating agents and acetylating agents are also suitable. Specific O-acylated precursor compounds include 3,5,5-tri-methylhexanoyloxybenzenesulfonates, benzoyloxybenzenesulfonates, cationic derivatives of the benzoyloxybenzenesulfonates, nonanoyl-6-aminocaproyloxybenzene sulfonates, monobenzoyltetraacetylglucose and pentaacetylglucose. Phthalic anhydride is a suitable anhydride-type precursor. Suitable and useful N-acyl compounds are described in GB-A-855735, 907356 and GB-A-1246338. Preferred imide type precursor compounds include N-benzoylsuccinimide, tetrabenzoylethylenediamine, N-benzoyl-substituted ureas and the N, N-N'N'-tetraacetylated alkylene diamines in which the alkylene group contains 1 to 6 carbon atoms, particularly the compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. A most preferred precursor compound is N, N-N ', N'-tetraacetylethylenediamine (TAED). The N-acylated precursor compounds of the lactam class are generally described in GB-A-955735. Although the broader aspect of the invention contemplates the use of any lactam useful as a peroxyacid precursor, the preferred materials comprise the caprolactams and valerolactams. Suitable caprolactam bleach precursors have the formula: g ^^^^^^^^^^^^^^^^^^ í | M »« fc g »» ^^^^^^^^^^ j wherein R1 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon atoms, preferably from 6 to 12 carbon atoms. Suitable valerolactams have the formula: wherein R1 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon atoms, preferably from 6 to 12 carbon atoms.

In highly preferred embodiments, R1 is selected from phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl and mixtures thereof. Other suitable materials are those which are normally solid at < 30 ° C, particularly the phenyl derivatives, ie, benzoylvalerolactam, benzoylcaprolactam and its substituted benzoyl analogs such as chloro, amino, nitro, alkyl, alkyl, aryl and alkyloxy derivatives. .and Z*. ^ ymk = é The caprolactam and valerolactam precursor materials in which the portion R1 contains at least 6, preferably from 6 to about 12 carbon atoms, provide peroxyacids in hydrophobic perhydrolysis which produce a nucleophilic cleansing and dirtiness of the body. The precursor compounds in which R1 comprises 1 to 6 carbon atoms provide hydrophilic bleaching species which are particularly efficient for bleaching beverage soils. Mixtures of "hydrophobic" and "hydrophilic" caprolactams and valerolactams, typically at weight ratios of 1.5 to 5: 1, preferably 1: 1, can be used herein for the mixed stain removal benefits. Another class of bleach precursor materials that is preferred includes cationic bleach activators, derivatives of the valerolactam and acylcaprolactam compounds of the formula: wherein x is 0 or 1, the substituents R, R 'and R "are each C1-C10 alkyl or C2-C4 hydroxyalkyl groups, or [(CyH2y) O] n -R'", where y = 2-4, n = 1-20 and R '"is a C1-C4 alkyl group or hydrogen, and X is an anion.

Suitable imidazoles include N-benzoyl imidazole and N-benzoylbenzimidazole, and other useful N-acyl group-containing peroxyacid precursors include N-benzoylpyrrolidone, dibenzoyltaurine and benzoylpyrglutamic acid. Another preferred class of bleach activator compounds are the amide-substituted compounds of the following general formulas: R 1 N (R 5) C (O) R 2 C (O) L or R 1 C (O) N (R 5) R 2 C (O) L wherein R 1 is an alkyl, alkylene, aryl or alkaryl group with from about 1 to about 14 carbon atoms, R 2 is an alkylene, arylene and alkarylene group containing from about 1 to 14 carbon atoms and R 5 is H or an alkyl group , aryl or alkaryl containing 1 to 10 carbon atoms and L can be essentially any leaving group. R1 preferably contains about 6 to about 12 carbon atoms. R2 preferably contains from about 4 to about 8 carbon atoms. R 1 may be straight or branched chain alkyl, substituted aryl or alkylaryl containing branching, substitution or both, and may be obtained either from synthetic sources or from natural sources, including for example, tallow grease. Analogous structural variations for R2 are permissible. The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other substituent groups or typical organic compounds. R5 is preferably H or methyl. R1 and R5 preferably should not contain more than 18 carbon atoms in total. Examples of bleach precursors of the above formulas that are preferred include the amide substituted peroxyacid precursor compounds selected from (6-octanamido-caproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzenesulfonate, and mixtures thereof as described in EP-A-0170386. Also suitable are benzoxazine-type precursor compounds, such as those described for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula: including the substituted benzoxazines type wherein Ri is H, alkyl, alkaryl, aryl, arylalkyl, secondary or tertiary amines, and wherein R 2, R 3, R and R 5 can be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxy, amino, alkyl, amino, COO c ß (where Re is H or an alkyl group) and carbonyl functions. v * * A benzoxazine type precursor which is especially preferred is: These bleach precursors can be partially replaced by preformed peracids such as N, N-phthaloylaminoperoxydic acid (PAP), peroxyadipic acid nonyl amide (NAPAA), 1,2-diperoxydodecanoic acid (DPDA) and trimethylammonium propenylimidoperoxymethyl acid (TAPIMA). Among the bleach precursors described above that are most preferred are the amide substituted bleach precursor compounds. Most preferably, the bleach precursors are the amide substituted bleach precursor compounds selected from (6-octanamido-caproyl) oxybenzenesulfonate, (6-nonamidocaproyl) oxybenzenesulfonate, (6-decanamidocaproyl) oxybenzenesulfonate and mixtures thereof. The bleach precursor can be found in any particulate form suitable for incorporation into a detergent composition, such as an agglomerate, granule, extrudate or spheronized extrudate. Preferably, the bleaching precursor is in the form of a spheronized extrudate. Preferred bleaching agents are solid sources of hydrogen peroxide. Preferred sources of hydrogen peroxide include prehydrated bleaches. The perhydrate is typically a perhydrated inorganic bleach, usually in the form of the sodium salt, as the source of alkaline hydrogen peroxide in the wash liquor. This perhydrate is usually incorporated at a level of from 0.1% to 60%, preferably from 3% to 40% by weight, most preferably from 5% to 35% by weight and more preferably from 8% to 30% by weight of the composition. The perhydrate may be any inorganic alkali metal salt such as monohydrated perborate or tetrahydrate, percabonate, perfosphate and persilicate salts, but is conventionally an alkali metal perborate or percarbonate. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2CO3.3H202, and is commercially available as a crystalline solid. The most commercially available material includes a low level of heavy metal sequestrant such as EDTA, 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) or an aminophosphonate, which is incorporated during the manufacturing process. For the purposes of the detergent composition aspect of the present invention, the percarbonate can be incorporated into the detergent compositions without There has been additional protection, but the preferred embodiments of said compositions use a coated form of the material. A variety of coatings can be used, including borate, boric acid and citrate or sodium silicate with an SiO2: Na2O ratio of about 1.6: 1 to 3.4: 1, preferably 2.8: 1, applied as an aqueous solution to give an level from 2% to 10%, (usually from 3% to 5%) of silicate solids by weight of the percarbonate. However, the most preferred coating is a mixture of sodium carbonate and sodium sulfate or chloride. The particle size scale of crystalline percarbonate is from 350 microns to 1500 microns, with an average of around 500-1000 microns. The non-aqueous detergent compositions of this invention may further comprise a surfactant and a liquid phase containing solvent of low polarity and having dispersed therein the bleach precursor composition. The components of the liquid and solid phases of the detergent compositions herein, as well as the form, preparation and use of the composition are described in greater detail as follows: All concentrations and ratios are on a weight basis, a unless otherwise indicated.

The surfactant mixture component amount of the non-aqueous liquid detergent compositions herein may vary depending on the nature and amount of the other components of the composition and depending on the desired rheological properties. of the composition finally formed. In general, this surfactant mixture will be used in an amount comprising from about 10% to 90% by weight of the composition. Most preferably, the surfactant mixture will comprise about 15% to 50% by weight of the composition. A typical list of anionic, nonionic, ampholytic and zwitterionic surfactants, and species of these surfactants, is given in the U.S. patent. 3,664,961 issued to Norris on May 23, 1972. The highly preferred anionic surfactants are linear alkylbenzenesulfonate (LAS) materials. Said surfactants and their preparation are described, for example, in U.S. Patents. 2,220,099 and 2,477,383 incorporated herein by reference. Linear straight sodium and potassium alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from 11 to about 14 are particularly preferred. C 9 -C 4 sodium LAS is preferred, for example, LAS of C12. Preferred anionic surfactants include the alkyl sulfate surfactants which are water soluble salts or acids of the formula ROSO 3M, wherein R is preferably a C 1 or C 2 hydrocarbyl, preferably an alkyl or hydroxyalkyl having one component C 1 -C 8 alkyl? SkU and preferably a C 12 -C 15 alkyl or hydroxyalkyl, and M is H or a cation, for example, an alkali metal cation (sodium, potassium, lithium) or amorphous or substituted ammonium cations ( quaternary ammonium cations such as tetramethylammonium cations and dimethylpiperidinium). Highly preferred anionic surfactants include the ethoxylated alkyl sulfate surfactants which are salts or water soluble acids of the formula RO (A) mSO3M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having an alkyl component of C?-C24, preferably a C 12 -C 8 alkyl or hydroxyalkyl, most preferably C 12 -Ci 5 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, most preferably between about 0.5 and about 3, and M is H or a cation which may be, for example, a metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.), cation of ammonium or substituted ammonium. Ethoxylated alkyl sulfates as well as propoxylated alkyl sulphates are contemplated herein. Specific examples of substituted ammonium cations include quaternary ammonium cations such as tetramethylammonium cations and dimethylpiperidinium. Exemplary surfactants are polyethoxylated alkyl sulfate (1.0) of C12-C-15 (C? 2-C? 5E (1.0) M) polyethoxylated alkyl sulfate (2.25) of C? 2-C15 (C12-C15E (2.25) M), polyethoxylated alkyl sulfate (3.0) of C12-C5 (Ci2-C15E (3.0) M) and polyethoxylated alkyl sulfate (4.0) of C12-C5 - ^ u ^? ' (C-i2-C-i5E (4.0) M), wherein M is conveniently selected from sodium and potassium. Other suitable anionic surfactants to be used are the alkyl ether sulfonate surfactants which include linear esters of C8-C20 carboxylic acids (ie, fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society" , 52 (1975), pp. 323-329. Suitable starting materials may include natural fatty substances such as those derived from tallow, palm oil, etc. The alkyl ether sulfonate surfactant which is preferred, especially for washing applications, comprises the alkyl ether sulfonate surfactants of the structural formula: wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof, R4 is a C-Cβ hydrocarbyl, preferably an alkyl or combination thereof, and M is a cation forming a water-soluble salt with the alkyl ether sulfonate. Suitable salt-forming cations include metals such as sodium, potassium and lithium and ammonium and substituted ammonium cations. Preferably, R3 is C10-C16 alkyl and R4 is a ^^^ ggSpS methyl, ethyl or isopropyl. Methyl ester sulfonates in which R3 is C10-C16 alkyl are especially preferred. Other anionic surfactants useful for detersive purposes may also be included in the laundry detergent compositions of the present invention. These may include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di-, and triethanolamine salts) of soap, C9-C20 linear alkylbenzenesulfonates, primary or secondary alkanesulfonates of C8- C22, C8-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by the sulfonation of the pyrolyzed product of alkaline earth metal citrates, for example, as described in the specification of British Patent No. 1, 082,179, C8-C24 alkyl polyglycol ether sulphates ( containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol atylene oxide sulfates, paraffinsulfonates, alkyl phosphates, isethionates such as acyl isethionates, N-acyltaurates, alkylsuccinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C12-C18 monoesters) and diesters of sulfosuccinates (especially unsaturated saturated C6-C12 diesters), alkylpolyacharide sulfates such as alkyl polyglycoside sulfates (unsulfated nonionic compounds described below) and alkylpolyethoxycarboxylates such as those of the formula RO (CH2CH2O) k-CH2COO -M +, wherein R is a C 8 -C 22 alkyl, k is an integer from 1 to 10 and M is a soluble salt-forming cation. The ft? ü &1? r ~ tt? iffl * Tp ~ • .¿a ^ & Colophonic acids and hydrogenated rosin acids are also suitable, such as rosin, hydrogenated rosin and rosin acids and hydrogenated rosin acids present in, or derived from tallow oil. Additional examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally described in the US patent. 3,929,678, issued December 30, 1975 to Laughlin et al., Column 23, line 58 to column 29, line 23 (incorporated herein by reference). When included therein, the detergent compositions of the present invention typically comprise from about 1% to about 40%, preferably from about 5% to about 25% by weight of said anionic surfactants. One class of nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic portion to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range of 8 to 17, preferably of 9.5 to 14, most preferably 12 to 14. The hydrophobic (lipophilic) portion can be aliphatic or aromatic in nature, and the length of the polyoxyethylene group that condenses with any particular hydrophobic group can be easily adjusted to produce a water-soluble compound that have the desired degree of balance between the hydrophilic and hydrophobic elements. - «yii? **** .. mmH? i ^^ Especially preferred nonionic surfactants of this type are ethoxylates of C9-C15 primary alcohol containing 3-12 moles of ethylene oxide per mole of alcohol, particularly the primary alcohols of C12-C-15 containing 5-8 moles of ethylene oxide per mole of alcohol. Another class of nonionic surfactants comprises the alkylpolyglucoside compounds of the general formula RO (CnH2nO) tZx wherein Z is a portion derived from glucose; R is a saturated hydrophobic alkyl containing from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; X is from 1.3 to 4, the compounds. they include less than 10% of the unreacted fatty alcohol and less than 50% of short chain alkyl polyglucosides. Compounds of this type and their use in detergents are described in EP-B 0 070 077, 0 075 996 and 0 094 118. Also suitable as nonionic surfactants are the polyhydroxy fatty acid amine surfactants of the formula: wherein R1 is H, or R1 is C-? 4, 2-hydroxyethyl hydrocarbyl, 2-hydroxypropyl or a mixture thereof, R2 is C5-31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, R1 is methyl, R2 is an alkyl or alkenyl chain of straight Cn.-is such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose in a reductive amination reaction.

NON-AQUEOUS LIQUID DILUENT To form the liquid phase of the detergent compositions, the surfactant (mixture) described hereinabove can be combined with a non-aqueous liquid diluent such as a liquid alcohol alkoxylated material or a non-aqueous low polarity organic solvent. .

Alkoxylated Alcohol A component of the liquid diluent suitable for forming the compositions herein comprises an alkoxylated alcohol material. Said materials are in turn also nonionic surfactants. These materials correspond to the general formula: R1 (CmH2mO) nOH jSS & wherein R1 is an alkyl group of C8-C-? 6, m is from 2 to 4, and n varies from about 2 to 12. Preferably, R1 is an alkyl group, which may be primary or secondary, containing about 9 to 15 carbon atoms, most preferably about 10 to 14 carbon atoms. Preferably, also the alkoxylated fatty alcohols will be ethoxylated materials containing about 2 to 12 portions of ethylene oxide per molecule, most preferably about 3 to 10 portions of ethylene oxide per molecule. The alkoxylated fatty alcohol component of the liquid diluent will often have a hydrophilic-lipophilic balance (HLB) ranging from about 3 to 17. Most preferably, the HLB of this material will vary from about 6 to 15, more preferably about 8 to 15. Examples of alkoxylated fatty alcohols useful as one of the essential components of non-aqueous liquid diluent in the compositions herein will include those which are made from alcohols of 12 to 15 carbon atoms containing about 7 moles of ethylene oxide. These materials have been marketed under the trade names Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company. Other useful Neodoles include Neodol 1-5, an ethoxylated fatty alcohol having an average of 11 carbon atoms in its alkyl chain with about 5 moles of ethylene oxide; Neodol 23-9, an ethoxylated primary C-? 2-C? 3 alcohol having about 9 moles of ethylene oxide and Neodol 91-10, a C9-Cn ethoxylated primary alcohol having about 10 moles of ethylene oxide . Ethoxylated alcohols of this type have also been marketed by Shell Chemical Company under the tradename Dobanol. Dobanol 91-5 is a fatty alcohol of C9-Cn ethoxylated with an average of 5 moles of ethylene oxide and Dobanol 25-7 is a fatty alcohol of C-12-C15 ethoxylated with an average of 7 moles of ethylene oxide per mole of fatty alcohol . Other examples of suitable ethoxylated alcohols include Tergitol 15-S-7 and Tergitol 15-S-9 both of which are ethoxylated linear secondary alcohols which have been marketed by Union Carbide Corporation. The first is a mixed ethoxylation product of linear Cn-C15 secondary alkanol with 7 moles of ethylene oxide and the latter is a similar product but with 9 moles of ethylene oxide being reacted. Other types of ethoxylated alcohols useful in the present compositions are the higher molecular weight nonionics, such as Neodol 45-11, which are similar products of condensation of ethylene oxide of higher fatty alcohols, being the higher fatty alcohol of 14-15 carbon atoms and the number of ethylene oxide groups per mole being of around 11. These products have also been marketed by Shell Chemical Company. The alkoxylated alcohol component when used as part of the liquid diluent in the non-aqueous compositions herein will generally be present to the extent of from about 1% to 60% by weight of the composition. Preferably, the alkoxylated alcohol component -aafe-afc. com will yield about 5% to 40% by weight of the compositions herein. More preferably, the alkoxylated alcohol component will comprise from about 10% to 25% the weight of the detergent compositions herein.

Low-polarity non-aqueous organic solvent Another component of the liquid diluent that can be part of the detergent compositions herein comprises non-aqueous, low polarity organic solvents. The term "solvent" is used herein to denote the non-surfactant vehicle or diluent portion of the liquid phase of the composition. Although one of the essential and / or optional components of the compositions herein can actually be dissolved in the "solvent" containing phase, other components will be present as dispersed particulate material in the "solvent" containing phase. In this way, the term "solvent" is not designed to require that the solvent material be capable of actually dissolving all of the detergent composition components added thereto. The non-aqueous organic materials that are used as solvents herein are those that are low polarity liquids. For the purposes of this invention, "low polarity" liquids are those that have very little, if any, tendency to dissolve one of the preferred types of particulate material used in the compositions herein, i.e., the agents Peroxygenated bleach, sodium perborate or sodium percabonate. In this way, relatively polar solvents such as ethanol should not be used. Suitable types of low polarity solvents useful in the non-aqueous liquid detergent compositions herein include lower alkylene glycol monoalkyl ethers, lower molecular weight polyethylene glycols, lower molecular weight methyl esters and amides, and the like. One type of non-aqueous solvent of low polarity which is preferred for use herein comprises the C2-C6 monoalkyl ethers of C2-C3 mono-, di-, tri- or tetraalkylene. Specific examples of such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropylene glycol monobutyl ether and dipropylene glycol monobutyl ether. Diethylene glycol monobutyl ether and dipropylene glycol monobutyl ether are especially preferred. Compounds of this type have been marketed under the trade names Dowanol, Carbitol and Cellosolve. Another preferred type of non-aqueous low polarity organic solvent useful herein comprises the lower molecular weight polyethylene glycols (PEGs). Said materials are those having molecular weights of at least about 150. PEGs of molecular weight varying from about 200 to 600 are more preferred. Another type of non-aqueous and non-polar solvent that is also preferred comprises the methyl esters of lower molecular weight. Said materials are those having the general formula: R1-C (O) -OCH3, wherein R1 ranges from 1 to about 18. Examples of suitable lower molecular weight methyl esters include methyl acetate, methyl propionate, octanoate of methyl and methyl dodecanoate. The non-aqueous low polarity organic solvents employed must, of course, be compatible and non-reactive with other components of the composition, eg, bleach and / or activators, used in the liquid detergent compositions herein. Said solvent component will generally be used in an amount of from about 1% to 60% by weight of the composition. Most preferably, the non-aqueous low polarity organic solvent will comprise about 5% 10 to 40% by weight of the composition, more preferably about 10% to 25% by weight of the composition.

Concentration of the liquid diluent As with the concentration of the surfactant mixture, the amount of the total liquid diluent in the compositions herein will be determined by the type and amounts of the other components of the composition, and by the desired properties of the composition. composition. Generally, the liquid diluent will comprise about 20% to 95% by weight of the compositions herein. Most preferably, the liquid diluent will comprise about 50% to 70% by weight of the composition.

Solid phase The non-aqueous detergent compositions herein may further comprise a solid phase of particulate material which is dispersed and suspended in the liquid phase. In general, said particulate material will vary in size from about 0.1 to 1500 microns. Most preferably, said material will vary in size from about 5 to 500 microns. The particulate material used herein may comprise one or more types of detergent composition components which, in particulate form, are substantially insoluble in the nonaqueous liquid phase of the composition. The types of particulate materials that can be used are described in detail as follows: Surfactants Another type of particulate material that can be suspended in the non-aqueous liquid detergent compositions herein includes anionic surfactants which are completely or partially insoluble in the non-aqueous liquid phase. The most common type of anionic surfactant with said solubility properties comprises primary or secondary alkyl sulfate anionic surfactants. Said surfactants are those produced by sulfation of higher C8-C2o fatty alcohols.

The conventional primary alkyl sulfate surfactants have the general formula: i z? ROÍ wherein R is typically a linear C8-C2o hydrocarbyl group, which may be straight or branched chain, and M is a water-solubilizing cation. Preferably, R is a C 1 -C alkyl, and M is alkali metal. Most preferably, R is approximately C12 and M is sodium. The conventional secondary alkyl sulfates can also be used as the essential anionic surfactant component of the solid phase of the compositions herein. Conventional secondary alkyl sulfate surfactants are those materials that have the sulfate portion distributed randomly along the hydrocarbyl "base structure" of the molecule. These materials can be illustrated by the structure: CH3 (CH2) n (CHOSO3-M +) (CH2) mCH3 wherein m and n are integers of 2 or more and the sum of m + n is typically from about 9 to 15, and M is a cation solubilizing in water. If they are used as all or part of the necessary particulate material, auxiliary anionic surfactants such as and ~ * & ~ and * and z «Jn»., ^. «Frte» -ÉÍÉ- ». .-Bfefe alkyl sulfates will generally comprise about 1% to 10% by weight of the composition, most preferably about 1% to 5% by weight of the composition. The alkyl sulfate used as all or part of the particulate material is prepared and added to the compositions herein separately from the non-alkoxylated alkylsulphate material which can be part of the alkyl ether sulfate surfactant component used essentially as part of the liquid phase of the present.

Organic detergency enhancing material Another possible type of particulate material that can be suspended in the non-aqueous liquid detergent compositions herein comprises an organic builder that counteracts the effects of calcium, or other ion, and the hardness of the water found. during the washing / bleaching use of the compositions herein. Examples of such materials include the alkali metals, citrates, succinates, malonates, fatty acids, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include the sodium, potassium and lithium salts of oxydisuccinic acid, melific acid, benzenepolycarboxylic acids and citric acid. Other examples of organic phosphonate sequestering agents are those that have been sold by Monsanto under the trade name Dequest and alkanehydroxyphosphonates. Citrate salts are much preferred.

Other suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties. For examplesaid materials include polyacrylic acid, polymaleic acid and suitable polyacrylic / polymaleic acid copolymers and their salts, such as those sold by BASF under the trademark Sokalan. Another suitable type of organic builder comprises the water soluble salts of higher fatty acids, ie, "soaps". These include alkali metal soaps such as the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably about 12 to about 18 carbon atoms. Soaps can be made by direct saponification of fats and oils, or by neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the fatty acid mixtures derived from coconut oil and tallow, that is, sodium or potassium tallow and coconut soap. If they are used as all or part of the necessary particulate material, the insoluble organic builders may generally comprise about 1% to 20% by weight of the compositions herein. Most preferably, said builder material may comprise about 4% to 10% by weight of the composition.

^ ¿^ Fe ^ fjj.

Inorganic Sources of Alkalinity Another possible type of particulate material that can be suspended in the non-aqueous liquid detergent compositions herein may comprise a material that serves to make the aqueous wash solutions formed from said compositions generally of an alkaline nature. Said materials may or may not also act as builders, that is, as materials that counteract the adverse effect of water hardness on the detergency performance. Examples of suitable alkalinity sources include the water soluble alkali metal carbonates, bicarbonates, borates, silicates and metasilicates. Although not preferred for ecological reasons, water-soluble phosphate salts can also be used as sources of alkalinity. These include the alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates. Of all these alkalinity sources, alkali metal carbonates such as sodium carbonate are preferred. The source of alkalinity, if it is in the form of a hydratable salt, can also serve as a desiccant in the non-aqueous liquid detergent compositions herein. The presence of an alkalinity source that is also a desiccant can provide benefits in terms of chemically stabilizing components of the composition such as the peroxygen bleaching agent that may be susceptible to water deactivation. tf-a-H-M- ^ lB-t-i-rfHÉ &iiiii If used as all or part of the particulate component, the source of alkalinity will comprise about 1% to 15% by weight of the compositions herein. Most preferably, the source of alkalinity may comprise about 2% to 10% by weight of the composition. Said materials, although water-soluble, will generally be insoluble in the non-aqueous detergent compositions herein. In this way, said materials will generally be dispersed in the non-aqueous liquid phase in the form of discrete particles.

Optional Components of the Composition In addition to the components of the liquid and solid phase of the composition as described hereinabove, the detergent compositions herein may, and preferably, contain several optional components. Such optional components may be in liquid or solid form. The optional components can be dissolved in the liquid phase or they can be dispersed within the liquid phase in the form of fine particles or droplets. Some of the materials that can optionally be used in the compositions herein are described in greater detail as follows: Optional organic additives The detergent compositions may contain an organic additive. An organic additive that is preferred is hydrogenated castor oil and its derivatives.

Hydrogenated castor oil is a commercially available product sold, for example, in several grades under the brand CASTORWAX.RTM. by NL Industries, Inc., Highstown, New Jersey. Other suitable hydrogenated castor oil derivatives are Thixcin R, Thixcin E, Thixatrol ST, Perchem R and Perchem ST. The hydrogenated castor oil that is especially preferred is Thixatrol ST. Castor oil can be added as a mixture with, for example, stearamide. The organic additive will partially dissolve in the non-aqueous liquid diluent. To form the structured liquid phase that is required for adequate phase stability and acceptable rheology, the organic additive is generally present to the extent of from about 0.05% to 20% by weight of the liquid phase. Most preferably, the organic additive comprises about 0.1% to 10% by weight of the non-aqueous liquid phase of the compositions herein. The organic additive is present in the total composition of about 0.05% to 2.5% by weight of the total detergent composition.

Optional inorganic detergency builders The compositions herein may also optionally contain one or more types of inorganic builders other than those listed hereinabove., that also work as sources of alkalinity. Such optional inorganic builders may include, for example, aluminosilicates such as zeolites. The aluminosilicate zeolites and their use as detergency builders are described in more detail in Corkill et al., U.S. Pat. No. 4,605,509; issued on August 12, 1986, the description of which is incorporated herein by reference. Also suitable for use in the detergent compositions herein are the layered crystalline silicates such as those described in this' 509 patent of E.U.A. If used, optional inorganic builders may comprise about 2% to 15% by weight of the compositions herein.

Optional Enzymes The detergent compositions herein may also optionally contain one or more types of detergent enzymes. Said enzymes may include proteases, amylases, cellulases and lipases. Such materials are known in the art and are also commercially available. Non-aqueous liquid detergents herein can be incorporated in the form of suspensions, "disks" or "pellets". Another suitable type of enzyme comprises those in the form of enzyme suspensions in nonionic surfactants. Enzymes in this form have been marketed, for example, by Novo Nordisk under the trade name "LDP". ^ - - ~ - - ^ - - ^ i- -. - * .. .., .., .. It is especially preferred in the present to use enzymes that are added to the compositions herein in the form of conventional enzyme pellets. Said pellets will generally vary in size from about 100 to 1,000 microns, most preferably around 200 to 800 microns and will be suspended throughout the non-aqueous liquid phase of the composition. It has been found that pellets in the compositions of the present invention, in comparison with other forms of enzyme, exhibit an enzyme stability especially desirable in terms of retention of enzymatic activity with the passage of time. Thus, compositions using enzyme pellets do not need to contain a conventional enzyme stabilization such as is most often used when the enzymes are incorporated in aqueous liquid detergents. If employed, the enzymes will normally be incorporated into the non-aqueous liquid compositions herein at levels sufficient to provide up to about 10 mg by weight, very typically about 0.01 mg to about 5 mg, of active enzyme per gram of the composition. In other words, the non-aqueous liquid detergent compositions herein will typically comprise about 0.001% to 5%, preferably about 0.01% to 1% by weight, of a commercial enzyme preparation. Protease enzymes, for example, are normally present in such commercial preparations at sufficient levels as Hjj ^^ ^ ¡^ jg ^ ¡to provide 0.005 to 0.1 Anson units (AU) of activity per gram of the composition.

Optional guelatary agents The detergent compositions herein may also optionally contain a chelating agent that serves to chelate metal ions, eg, iron and / or manganese, in the non-aqueous detergent compositions herein. Said chelating agents then serve to form complexes with metal impurities in the composition that would otherwise tend to deactivate components of the composition such as the peroxygen bleaching agent. Useful chelating agents can include aminocarboxylates, phosphonates, aminophosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof. Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethyl-ethylene-diaminotriacetates, nitrotriacetates, ethylenediaminetetrapropionates, triethylenetetraminohexacetates, diethylenetriaminepentaacetates, ethylenediamine disuccinates and ethanoldiglycins. The alkali metal salts of these materials are preferred. Aminophosphonates are also suitable for use as chelating agents in the compositions of this invention, when at least low levels of total phosphorus are allowed in the detergent compositions, and include ethylene glycotetrakis (methylene phosphonates) as DEQUEST Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. Preferred chelating agents include hydroxyethyl diphosphonic acid (HEDP), diethylenetriaminepentaacetic acid (DTPA), ethylenediamine disuccinic acid (EDDS) and dipicolinic acid (DPA) and salts thereof. The chelating agent can, of course, also act as a builder during the use of the compositions herein for washing / bleaching fabrics. The chelating agent, if employed, may comprise about 0.1% to 4% by weight of the compositions herein. Most preferably, the chelating agent will comprise from about 0.2% to 2% by weight of the detergent compositions herein.

Optional thickening, viscosity control and / or dispersing agents The detergent compositions herein may also optionally contain a polymeric material which serves to improve the ability of the composition to maintain its components in solid particles in suspension. Said materials can then act as thickeners, viscosity control agents and / or dispersing agents. Such materials are often polymeric polycarboxylates, but may include other polymeric materials such as polyvinylpyrrolidone.

JU ".-AI-Bfe- ,., AFEAS ¿, '.. -... ^ Z - (PVP) and polymeric amine derivatives such as ethoxylated hexamethylene diamines and quaternized Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing. suitable unsaturated monomers, 5 preferably in its acid form. unsaturated monomeric acids that 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 of monomeric segments is adequate in The polymeric polycarboxylates of the present invention do not contain carboxylate radicals such as vinyl methyl ether, styrene, ethylene, etc., as long as said segments do not constitute more than about 40% by weight of the polymer. Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Said acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of said polymers in acid form preferably ranges from about 2,000 to 10,000, most preferably about 4,000 to 7,000, and more preferably about 4,000 to 5,000. The water-soluble salts of said acrylic acid polymers may include, for example, the alkali metal 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, patent of E.U.A. No. 3,308,067 issued March 7, 1967. Such materials also perform a detergency builder function. If used, the optional thickening, viscosity control and / or dispersing agents should be present in the compositions herein to the degree of about 0.1% to 4 by weight. Most preferably, said materials may comprise about 0.5% a 2% by weight of the detergent compositions herein.

Polishes, foam suppressors and / or optional perfumes The detergent compositions herein may also optionally contain brighteners, suds suppressors, silicone oils, bleach catalysts and / or conventional perfume materials. Such brighteners, suds suppressors, silicone oils, bleach catalysts and perfumes must, of course, be compatible and non-reactive with the other components of the composition in a non-aqueous environment. If present, the brighteners, foam suppressors and / or perfumes will typically comprise about 0.01% to 4% by weight of the compositions herein.

FORM OF COMPOSITION The liquid detergent compositions containing particles of this invention have a substantially non-aqueous (or anhydrous) character. Although very small amounts of water can be incorporated in said As compositions as an impurity in the essential or optional components, the amount of water should not by any means exceed about 5% by weight of the compositions herein. Most preferably, the water content of the non-aqueous detergent compositions herein will comprise less than about 1% by weight. The non-aqueous detergent compositions containing particles herein will be in the form of a liquid.

Preparation and use of the composition The non-aqueous liquid detergent compositions herein can be prepared by mixing a non-aqueous liquid phase and subsequently adding to this phase additional particulate components in any convenient order and mixing, for example, by stirring, the combination of components resulting to form the stable phase compositions of the present. In a typical procedure for preparing said compositions, certain essential and preferred optional components will be combined in a particular order and under certain conditions. In a first step of a preferred preparation process, the liquid phase containing anionic surfactant is prepared. This preparation step includes the formation of an aqueous suspension containing about 30 to 60% of one or more alkali metal salts of linear C10-C16 alkylbenzenesulfonic acid and about 2-15% of one or more non-surfactant salts. . In a subsequent step, this suspension is dried to the extent necessary to form a solid material containing less than about 4% by weight of residual water. After the preparation of this solid material containing anionic surfactant, this material can be combined with one or more of the non-aqueous organic diluents to form the liquid phase containing the surfactant of the detergent compositions herein. This is done by reducing the anionic surfactant-containing material formed in the pre-preparation step described above in powder form and combining said powder material with a stirred liquid medium comprising one or more of the non-aqueous organic diluents, either surfactant or non-surfactant, or both, as described hereinabove. This combination is carried out under stirring conditions which are sufficient to form a completely mixed dispersion of particles of the insoluble fraction of the LAS / co-dried salt material along a non-aqueous organic liquid diluent. In a subsequent processing step, the particulate material to be used in the detergent compositions herein can be added. Such components, which can be added under high shear agitation, include any optional surfactant particles, particles of substantially all of an organic builder, for example, citrate and / or fatty acid and / or source of alkalinity, for example, Sodium carbonate can be added by continuing to maintain this mixture of composition components under agitation by shear stress. The agitation of the mixture is continued, and if necessary, it can be increased at this point to form a uniform dispersion of insoluble solid phase particulate materials in the liquid phase. The non-aqueous liquid dispersion prepared in this way can be subjected to pulverization or shear agitation. Spraying conditions will generally include maintaining a temperature between about 10 and 90 ° C, preferably between 20 ° C and 60 ° C. The equipment suitable for this purpose includes agitated ball mills, two-ball mills (Fryma), colloidal mills, high pressure homogenizers, high shear mixers and the like. The colloid mill and high shear mixers are preferred for their high output speed and low maintenance costs. The small particles produced in said equipment will generally vary in size from 0.4-150 microns. The agitation is continued later, and if necessary, it can be increased at this point to form a uniform dispersion of insoluble solid phase particles in the liquid phase. In a second processing step, the particles of the bleach precursor are mixed with the suspension of the first step of mixed in a second mixing step. This mixture is then subjected to wet pulverization in such a way that the average particle size of the bleach precursor is less than 600 microns, preferably between 50 and 500 microns, most preferably between 100 and 400 microns.

After some or all of the above solid materials have been added to this stirred mixture, the particles of the highly preferred peroxygen bleach agent can be added to the composition, again while the mixture is maintained under shear agitation. . In a third processing step, the activation of the organic additive is obtained. The organic additives are subjected to wetting and dispersing forces to reach a dispersed state. It is within the ability of an expert in the art to activate the organic additive. The activation can be done according to the one described by Rheox, in the Rheology Handbook, A practical guide to rheological additives. There are basically three different stages. The first step is to add the agglomerated powder to the solvent. This combination is carried out under conditions of agitation (shear, heat, stage 2) which are sufficient to lead to complete de-agglomeration. With continuous agitation and heat development over a period of time, the solvent-swollen particles of the organic additive are reduced to their active state in step 3. By adding solid components to the non-aqueous liquids according to the above procedure, it is advantageous to keep the moisture content unbound and free of these solid materials below certain limits. The moisture in said solid materials is frequently present at levels of 0.8% or more (see the method described below). By reducing the free moisture content, for example, by bed drying ^^ - - ^ * "• - - - • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • Fluidized, from solid particulate materials at a free moisture level of 0.5% or less before incorporation into the detergent composition matrix, stability benefits can be obtained significant for the resulting composition.

Determinations of free and total water For the purposes of this patent application, and without wishing to be bound by theory, reference is made to "free water" as the amount of water that can be detected after the removal of the solid components and not dissolved in the product, while "total water" refers to the amount of water that is present in the product as a whole, whether it is bound to solids (for example, water of hydration), dissolved in the liquid phase or in any other shape. One method of determining water that is preferred is the so-called "Karl Fischer titration" method. Other Karl Fischer titration methods, for example, NMR, microwave or IR spectrometry may also be suitable for the determination of water in the liquid part of the product and in the complete product as described below. The "free water" of a formulation is determined in the following manner. At least one day after the preparation of the formula (to allow equilibration), a sample is subjected to centrifugation until a transparent layer is obtained visually and free of solid components. This transparent layer is separated from the solids, and a heavy sample is introduced directly into a vessel for coulometric Karl Fischer titration. The water level determined in this way (mg of water / kg of transparent layer) is known as "free water" (in ppm). The "total water" is determined by first extracting a heavy amount of the finished product with a polar and anhydrous extraction liquid. The extraction liquid is selected in such a way that interferences of undissolved solids are minimized. In many cases, dry methanol is a preferred extraction liquid. Normally, the extraction procedure reaches an equilibrium within a few hours - the previous requires validation for different formulations - and can be accelerated by sonification (ultrasonic bath). After that time, a sample of the extract is centrifuged or filtered to remove the solids, and a known aliquot is then introduced into the Karl Fischer titration cell (coulometric or volumetric). The value found in this way (mg of water / kg of product) is referred to as the "total water" of the formulation. Preferably, the non-aqueous liquid detergent compositions of the present invention comprise less than 5%, preferably less than 3%, most preferably less than 1% free water.Viscosity and Relaxation Measurements The non-aqueous liquid detergent compositions containing particles herein will be relatively viscous and phase stable under conditions of commercialization and use of said compositions.

Frequently, the viscosity of the compositions herein will vary from about 300 to 10,000 cps, most preferably around 500 to 3000 cps. The physical stability of these formulations can also be determined by relaxation measurements. Frequently, the relaxation of the compositions herein will vary from about 1 to 5 Pa, most preferably around 1.5 to 10 Pa. For the purpose of this invention, viscosity and relaxation are measured with a Carri-Med CSL2100 rheometer according to the invention. with the method described later. The rheological properties were determined by a constant voltage rheometer (Carri-Med CSL2100) at 25 ° C. One was used parallel plate configuration with a disc radius of 40 mm and a layer thickness of 2 mm. The shear stress varied between 0.1 Pa and 125 Pa. The reported viscosity was the value measured at a shear rate of about 20 s "1. The effort at loosening was defined as the previous effort whose disk movement was detected This implies that the shear rate was below 3 x 10"4 s' Measurements of gas evolution velocity: Gas evolution velocities (GERs) can be measured by placing a product sample (usually 1000-1200 20 g) in an Erlenmeyer that can be gas-tight by means of an adapter and a valve. The product is then stored at a constant temperature (usually 35 ° C), and connected to a gas burette. After a certain time (usually 1-10 days), the valve was opened and the difference in iMHi? r ^ Mi ^^ i «-Í -« - Í-í-M - l-i-ri- ^ volume. To minimize the effects of environmental pressure changes, the values are referenced against a sample that does not contain bleach. In general, the GER of the liquid detergent compositions contains Y% of a bleaching agent, said bleaching agent has a product GER of Z ml / day / kg at 35 ° C, must be less than 0.008 of the product Y x Z ml / day / kg at 35 ° C. The compositions of this invention, prepared as described hereinabove, can be used to form aqueous wash solutions for use in washing and bleaching fabrics. In general, an effective amount of said compositions is added to water, preferably in a conventional automatic laundry washing machine, to form said aqueous washing / bleaching solutions. The aqueous wash / bleach solution formed in this manner is then contacted, preferably under agitation, with the fabrics which will be washed and bleached therewith. An effective amount of the liquid detergent compositions herein added to water to form the aqueous wash / bleach solutions may comprise sufficient amounts to form about 500 to 8,000 ppm of the composition in aqueous solution. Most preferably, about 800 to 5,000 ppm of the detergent compositions herein will be provided in the aqueous wash / bleach solution.

The following examples illustrate the preparation and performance advantages of the non-aqueous liquid detergent compositions of the present invention. However, said examples do not necessarily attempt to limit or otherwise define the scope of the present invention.

EXAMPLE I Preparation of a non-aqueous liquid detergent composition 1) Part of the butoxy-propoxy-propanol (BPP) and a non-ionic ethoxylated alcohol surfactant CnEO (5) (Genapol 24/50) are mixed for a short time (1-5 minutes) using a paddle impeller in a mixing tank in a single phase. 2) LAS is added to the BPP / NI mixture after heating the BPP / NI mixture to 45 ° C. 3) If required, the liquid base (LAS / BPP / NI) is pumped into drums. Molecular sieves (type 3A, 4-8 meshes) are added to each drum at 10% of the net weight of the liquid base. The molecular sieves are mixed in the liquid base using individual paddle turbine mixers and drum spinning techniques. The mixing is carried out under a cover of nitrogen to prevent the collection of moisture from the air. The total mixing time is 2 hours, after which 0.1-0.4% of the moisture in the liquid base is removed. The molecular sieves are removed by passing the liquid base through a 20-30 mesh screen. The liquid base is returned to the mixing tank. 4) The additional solid ingredients are prepared for addition to the composition. Such solid ingredients include the following: Sodium carbonate (particle size 100 microns) Sodium citrate dihydrate Maleic acrylic copolymer (BASF Sokalan) Brightener (Tinopal PLC) Tetrasodic hydroethylidene diphosphonic acid salt (HEDP) Sodium diethylenetriaminepentamethylenephosphonate Ethylenediamine disuccinic acid (EDDS) These solid materials, which are all sprayable, are added to the mixing tank and mixed with the liquid base until uniform. This takes about 1 hour after the addition of the last powder. The tank is covered with nitrogen after the addition of the powders.

A particular order of addition for these powders is not critical. 5) The batch is pumped once through a Fryma colloid mill, which has a simple rotor-stator configuration in which a high-speed rotor rotates within a stator that creates a zone of high shear stress. This reduces the particle size of all solids. This leads to an increase in the performance value (ie, structure). The batch is then reloaded into the mixing tank after cooling. 6) The bleach precursor particles are mixed with the spray suspension of the first mixing step in a second mixing step. This mixture is then subjected to wet pulverization in such a way that the average particle size of the bleach precursor is less than 600 microns, preferably between 50 to 500 microns, most preferably between 100 and 400 microns. 7) Other solid materials may be added after the first processing step. These include the following: Sodium percarbonate (400-600 microns) Protease enzyme, cellulase and amylase pellets (400-800 microns, specific density less than 1.7 g / mL) Titanium dioxide particles (5 microns) Catalyst These materials Non-sprayable solids are then added to the mixing tank followed by the liquid ingredients (perfume and suds suppressor based on silicone, fatty acid / silicone). The batch is then mixed for one hour (under a nitrogen blanket). 8) As a final step of the formulation, the hydrogenated castor oil was added to part of the BPP to a colloid mixture at high speed, the dispersion was heated to 55 ° C. The shear time was around one hour. The resulting composition has the formula described in table 1.

-M "rtrth * taft" É feS ^ j | The catalyst was prepared by adding starch modified with octenylsuccinate, to water in the approximate ratio of 1: 2. The catalyst is then added to the solution and mixed until dissolved. The composition of the solution is: catalyst 5% starch 32% (starch includes 4-6% bound water) water 63% The solution is then spray-dried using a Niro Atomizer laboratory spray dryer. The inlet of the spray dryer is set at 200 ° C, and the atomization air is around 4 bar. The drop in air pressure in the procedure is 30-35 mm of water. The feed rate of the solution is set to obtain an exit temperature of 100 ° C. The powder material is collected at the base of the spray dryer. The composition is: Catalyst 15% starch (and bound water) 85% The particle size is 15 to 100 μm leaving the dryer.

TABLE 1 Non-aqueous liquid detergent composition with bleach Component% by weight of% by weight of active active salt Sodium salt of LAS 16 15 Ethoxylated alcohol C11 EO = 5 21 20 BPP 19 19 Sodium citrate 4 5 Sodium salt of [4- [N-nonanoyl-6-6-7-aminohexanoyloxybenzenesulfonate] 1,2-methoxethylenediamine chloride salt quaternized with methyl Ethylenediamine disuccinic acid 1 1 Sodium carbonate 7 7 Maleic Acrylic Copolymer 3 3 Protease pellets 0.40 0.4 Amylase pellets 0.8 0.8 Cellulase Pellets 0.50 0.5 Sodium percarbonate 16 - Sodium perborate - 15 1.5 1.5 foam suppressor Perfume 0.5 0.5 Titanium dioxide 0.5 0.5 Brightener 0.14 0.2 Thixatrol ST 0.1 0.1 Catalyst 0.03 0.03 Motas 0.4 0.4 Miscellaneous ingredients up to 100% The resulting composition of Table 1 is a structured, stable, pourable and anhydrous heavy-duty liquid laundry detergent that provides excellent stain and dirt removal performance when used in normal fabric washing operations. The viscosity measurement at 25 ° C is around 2200cps at effort velocity -j * s b¿í aitmi. cutting 20 s "1, the yield is about 8.9 Pa at 25 ° C. The GER is less than 0.35 ml / day / kg at 35 ° C. A 720 ml bottle, filled with 660 ml of product did not show a bulge significant even after 6 weeks of storage at 35 ° C.

Claims (5)

NOVELTY OF THE INVENTION CLAIMS

1. - The non-aqueous liquid detergent compositions comprising a bleach precursor and / or a bleaching agent further comprising a compound that is capable of interacting with the oxygen released by the decomposition of the bleach precursor and / or bleaching agent. 2.- Non-aqueous liquid detergent compositions according to claim 1 comprising a bleaching precursor and / or a bleaching agent and further comprising an oxygen scavenger. 3.- Liquid non-aqueous detergent compositions according to claims 1-2, further characterized in that said oxygen scavenger contains a metal ion. 4.- Non-aqueous liquid detergent compositions according to claims 1-3, further characterized in that said metal ion is selected from iron, cobalt and manganese. 5.- Liquid non-aqueous detergent compositions according to claims 1-4, further characterized in that said metal ion forms part of a catalyst. airii ^^ jjta Ug