EP1129164A1 - Bleach compositions - Google Patents

Abstract

The present invention relates to bleaching, pre-soak, pre-treatment, and laundry detergent compositions comprising: A) a catalytically effective amount of a transition-metal bleach catalyst which is a complex of a transition-metal and a cross-bridged macropolycyclic ligand, for example, 5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2] hexadecane manganese (II) chloride, having formula (1); and B) the balance carriers and other adjunct ingredients; provided said composition is substantially free of any organic or inorganic peroxygen compounds.

Description

BLEACH COMPOSITIONS

FIELD OF THE INVENTION The present invention relates to bleaching and detergent compositions which comprise a catalytically effective amount of a transition-metal bleach catalyst which is a complex of a transition-metal and a cross-bridged macropolycyclic ligand The present invention further relates to a method for bleaching/cleaning fabπc with a catalytically effective amount of said transition-metal bleach catalyst wherein the method is performed substantially free of any organic or inorganic peroxygen compound or precursors to any organic or inorganic peroxygen compound

BACKGROUND OF THE INVENTION

Bleaching of fabric is essentially exposing soiled or stained fabπc to a chemical reaction the purpose of which is to eliminate the soil or stain. At one point ι, ι time, bleaching involved exposure of fabπc to a solution of hypochloπte. Therefore, fabric which was colored or dyed via sensitive pigments were excluded from treatment with bleach. To the benefit of the consumer, formulators developed various forms of bleach inter aha peroxygen bleaching systems which typically comprise a source of hydrogen peroxide and a bleach activator. This combination of source of hydrogen peroxide and activator plays a dominating role in effective, safe bleaching compositions. An effective example of this peroxygen bleaching system employs perborate

(peroxygen source) and nonanoyloxybenzene sulfonate (activator).

In order to boost the performance of bleaching agents and to develop bleaching systems which are safe to any type of dyed or colored fabric inter alia silk, polyester blends, cotton, nylon, formulators have continued to develop peroxygen bleaching systems, as well as new methods of forming activated oxygen.

However, there still remains a need in the art for a bleaching system which will effectively bleach fabπc without the need for reactive chemicals such as peroxides, sources of peroxide, and/or mixtures thereof.

SUMMARY OF THE INVENTION The present invention meets the aforementioned needs in that it has been surprisingly discovered that bleaching of soils and stains can be accomplished in the absence of a source of hydrogen peroxide or other peroxygen bleaching agent. In other words, it has been surprisingly discovered that effective bleaching of soils and stains can be accomplished solely with a transition-metal bleach catalyst according to the present invention.

A first aspect of the present invention relates to bleaching compositions comprising:

A) a catalytically effective amount of a transition-metal bleach catalyst which is a complex of a transition-metal and a cross-bridged macropolycyclic ligand; and

B) the balance earners and other adjunct ingredients; provided said composition is substantially free of any organic or inorganic peroxygen compounds.

The present invention further relates to a method for cleaning and/or bleaching soils and stams on fabrics, said method comprising the step of contacting the fabric m need of cleaning and/or bleaching with an aqueous solution containing a composition which is substantially free of a peroxygen source and which comprises: a) a catalytically effective amount of a transition-metal bleach catalyst which is a complex of a transition-metal and a cross-bridged macropolycyclic ligand; and b) the balance earners, fillers, and other adjunct ingredients; provided the concentration of said transition metal bleach catalyst in the aqueous solution is at least about 0.01 ppb and said composition is substantially free of any organic or inorganic peroxygen compounds.

The compositions and methods of the present invention are suitable for cleaning/bleaching any surface in need of stain removal. For example, hard surface cleaners and automatic dishwashing compositions can employ the bleach catalysts of the present invention in applications which are substantially free of any organic or inorganic peroxygen compounds.

These and other objects, features, and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed descπption and the appended claims.

All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (° C) unless otherwise specified. All documents cited are in relevant part, incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the surprising discovery that bleaching of soils and stains can be accomplished by a transition-metal catalyst in the absence an added peroxygen bleach. Sources of peroxygen bleaches include, but are not limited to. sources of hydrogen peroxide inter alia hydrogen peroxide, percarbonate, perborate. Alkali metal and alkaline earth metal percarbonate and perborate are typically found in laundry bleaching systems. These sources of hydrogen peroxide are typically formulated with one or more bleach activators inter aha nonanoyloxybenzenesulfonate (NOBS), tetraacetylethylenediamme (TAED). Bleach activators are typically viewed as precursors to the less stable but more reactive peroxyacid bleaching agents Peroxyacids are formed in situ when the bleach activator (peroxyacid precursor) reacts with hydrogen peroxide or hydroperoxide anion via a perhydrolysis reaction

In addition, peroxyacids can comprise a peroxygen bleaching system. Although these systems do not have the range of formulatabihty now enjoyed by systems such as NOBS/perborate, nevertheless, suitable methods for formulating peroxyacids inter aha the amido peroxyacid, NAPAA, as described m U S. 5.536.435 Chapman et al., issued July 16, 1996 included herein by reference. Absence of Peroxygen Sources The compositions of the present invention, as well as the methods for cleaning and/or bleaching of fabric which utilize the compositions of the present invention are substantially free of any peroxygen source such as hydrogen peroxide, peroxyacid etc. The compositions of the present invention need only have an effective amount of the herein below described catalyst present for effective bleaching. For the purposes of the present invention the term "substantially free" is defined as "the formulator does not include in the composition any peroxygen compound or source of peroxygen at a level required for either effective bleaching without a transition metal catalyst, or which would provide an increase m effectiveness of bleaching in the presence of a transition metal catalyst as defined herein." Therefore, as will be further described herein below, effective bleaching of stains can be accomplished by simply adding an aqueous or non-aqueous solution of a catalyst as described herein to fabπc which is stained, preferably the fabπc is m an aqueous solution when contacted with the catalyst. However, it is recognized that because of factors outside the control of the formulator inter aha source of product raw materials, unwanted decomposition of one or more ingredients, that a source of peroxygen may be introduced and/or formed unknowingly in the product. The compositions of the present invention do not require any peroxygen source, but the presence of any minor amounts will not effect the performance of the bleaching compositions described herein.

Formulators may typically include a small amount of a source of hydrogen peroxide into compositions for the purposes of stabilizing enzymes, for example, a minor amount of perborate may be added. However, this amount of perborate is typically so minor that it has no effect on the bleaching capacity of the compositions of the present invention. In cases where the formulator has added a minor amount of an oxidant, or other source of peroxide for the purposes of stabilizing an adjunct ingredient, for the purposes of the present invention, those compositions are still defined as "substantially free" of a source of peroxygen as defined herein above if they do not provide additional bleaching activity on stains under typical use conditions. For example, a "substantially free" composition can include an amount of peroxygen source provided the degree to which the catalyst is effective is substantially the same as if the source of peroxygen were absent. For the purposes of the present invention, any composition which comprises less than 0.1%, preferably less than 0.01% of a primary oxidant, such as a pre-formed peracid or a source of hydrogen peroxide is considered "substantially free" as further defined herein above Additionally, any laundry liquor, laundry wash water, pre-soak bath, or other fabπc or surface cleaning solution, wherein the present catalysts are used and which comprises less than 0 001% by weight of a source of peroxygen, pre-formed or otherwise formed in situ, is defined herein as "substantially free" as defined herein above. Stated otherwise, if the catalysts of the present invention are used to bleach stains on fabric, or otherwise clean/bleach a hard surface or dishware, and the solution containing the catalyst has a concentration of a source of peroxygen less than 0.001%, that solution is defined herein as "substantially free" of a source of peroxygen. Bleach Catalyst

The compositions of the present invention comprise an effective amount of a bleach catalyst. The term "an effective amount" is defined as "an amount of the transition-metal bleach catalyst present in the present invention compositions, or duπng use according to the present invention methods, that is sufficient, under whatever comparative or use conditions are employed, to result in at least partial oxidation of the material sought to be oxidized by the composition or method." Typically the material to be oxidized is an unwanted substance inter alia food and beverage stains, greasy/oily stains, body soils on fabric, however, this is not the limitation to which the invention is applicable. Oxidation m the absence of a source of peroxygen has wide applicability and the present invention is not limited solely to bleaching and/or cleaning of fabric. For example, automatic dishwashing compositions are an embodiment of the present invention wherein bleaching of a stain with a composition and/or with a solution which is "substantially free" of a source of peroxygen is a part of the present invention. The same is equally true for hard surface cleaning compositions and solutions which comprise hard surface cleaning compositions which are "substantially free" of a source of peroxygen.

Preferably the compositions of the present invention compπse from about 1 ppb (0.0000001%o), more preferably from about 100 ppb (0.00001%), yet more preferably from about 500 ppb (0.00005%), still more preferably from about 1 ppm (0.0001%) to about 99.9%, more preferably to about 50%. yet more preferably to about 5%, still more preferably to about 500 ppm (0.05%) by weight of the composition, of a transition-metal bleach catalyst as described herein below In the broadest view, the transition-metal bleach catalyst of the present invention comprises l) a transition metal selected from the group consisting of Mn(II), Mn(III), Mn(IV),

Mn(V), Fe(II), Fe(III), Fe(IV), Co(I), Co(II), Co(III), Nι(I), Nι(II), Nι(III), Cu(I),

Cu(II), Cu(III), Cr(II), Cr(III), Cr(IN), Cr(V), Cr(VI), V(ffl). V(IV). V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(III), and

Ru(IV), preferably Mn(II), Mn(III), Mn(IV), Fe(II), Fe(ffl). Fe(IV), Cr(II),

Cr(ffl), Cr(IV), Cr(V), Cr(VI), and mixtures thereof, n) a cross-bridged macropolycyclic ligand being coordinated by four or five donor atoms to the same transition metal, said ligand comprising- a) an organic macrocycle ring containing four or more donor atoms

(preferably at least 3, more preferably at least 4, of these donor atoms are Ν) separated from each other by covalent linkages of 2 or 3 non-donor atoms, two to five (preferably three to four, more preferably four) of these donor atoms being coordinated to the same transition metal atom m the complex; b) a cross-bridged chain which covalently connects at least 2 non-adjacent donor atoms of the organic macrocycle ring, said covalently connected non-adjacent donor atoms being bridgehead donor atoms which are coordinated to the same transition metal in the complex, and wherein said cross-bridged chain comprises from 2 to about 10 atoms (preferably the cross-bπdged chain is selected from 2, 3 or 4 non-donor atoms, and

4-6 non-donor atoms with a further donor atom); and in) optionally, one or more non-macropolycychc hgands, preferably selected from the group consisting of H2O, ROH, ΝR3, RCN, OH^", OOH^", RS^", RO^", RCOO^", OCN^", SCN^", N3^", CN^", F^", Cl^", Br^", I^", O2^", NO3^", NO2^", SOzi^2", SO3^2", PO4^3", organic phosphates, organic phosphonates, organic sulfates, organic sulfonates, and aromatic N donors such as pyπdines, pyrazines, pyrazoles, lmidazoles, benzimidazoles, pyπmidines, tπazoles and thiazoles with R being H, optionally substituted alkyl, optionally substituted aryl. The preferred cross-bridged macropolycyclic hgands are is selected from the group consisting of: a) a cross-bπdged macropolycyclic ligand of formula (I) having denticity of 4 or 5'

(I); b) a cross-bridged macropolycyclic ligand of formula (IT) having denticity of 5 or 6:

(π); c) the cross-bπdged macropolycyclic ligand of formula (HI) having denticity of 6 or 7:

(in); wherein each E unit represents the moiety having the formula.

(CR_n)_a-X-(CR_n)_a. wherein X is selected from the group consisting of oxygen, sulfur, -NR-, phosphorous, or X represents a covalent bond wherein E has the formula:

(CR_n)_a-(CR_n)_a' for each E units the sum of a + a' is independently selected from 1 to 5; each G unit is a moiety (CR_n)tø, each R unit is independently selected from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl, and heteroaryl, or two or more R units are covalently bonded to form an aromatic, heteroaromatic, cycloalkyl, or heterocycloalkyl ring; each D unit is a donor atom independently selected from the group consisting of nitrogen, oxygen, sulfur, and phosphorous, and at least two atoms which comprise D units are bridgehead donor atoms coordinated to the transition metal; B units are a carbon atom, a D unit, or a cycloalkyl or heterocychc ring; each n is an integer independently selected from 1 and 2, completing the valence of the carbon atoms to which the R units are covalently bonded; each n' is an integer independently selected from 0 and 1 , completing the valence of the D donor atoms to which the R moieties are covalently bonded; each n" is an integer independently selected from 0, 1, and 2 completing the valence of the B atoms to which the R moieties are covalently bonded; each a and a' is an integer independently selected from 0 to 5, wherein the sum of all a + a' values m the ligand of formula (I) is within the range of from about 8 to about 12; the sum of all a + a' values in the ligand of formula (II) is within the range of from about 10 to about 15; and the sum of all a + a' values m the ligand of formula (III) is within the range of from about 12 to about 18: each b is an integer independently selected from 0 to 9, or in any of the above formulas, one or more of the (CR_n)tø moieties covalently bonded from any D to the B atom is absent as long as at least two (CRn)}-, covalently bond two of the D donor atoms to the B atom m the formula, and the sum of all b indices is within the range of from about 2 to about 5.

A further description of the bleach catalysts of the present invention can be found in WO

98/39406 Al , published September 1 1 , 1998, WO 98/39098 Al , published September 1 1 , 1998, and WO 98/39335 Al, published September 1 1, 1998, all of which are included herein by reference

The nomenclature used throughout this patent to describe the transition-metal bleach catalysts is the same nomenclature style used in the above-identified references. However, the chemical names of one or more of the herein described hgands . y from the chemical name assigned under the rules of the International Union of Pure and Applied Chemistry (IUPAC). For example, a preferred ligand for the purposes of the present invention, 5,12-dιmethyl-l ,5,8, 12- tetraaza-bιcyclo[6.6.2]hexadecane, has the IUPAC name 4,l l-dιmethyl-l,4,8,l l-tetraaza- bιcyclo[6.6.2]hexadecane. A further preferred ligand is 5,12-dιethyl-l,5,8, 12-tetraaza- bιcyclo[6.6.2]hexadecane. Transition-metal bleach catalysts useful in the invention compositions can in general include known compounds where they conform with the invention definition, as well as. more preferably, any of a large number of novel compounds expressly designed for the present laundry or cleaning uses. Non-limiting examples of suitable catalysts according to the present invention include: Dιchloro-5,12-dιmethyl-l,5,8,12-tetraazabιcyclo[6.6.2]hexadecane Manganese(II) Dιchloro-4, 10-dιmethyl- 1 ,4,7, 10-tetraazabιcyclo[5.5.2]tetradecane Manganese(II) Dιaquo-5,12-dιmethyl-l,5,8,12-tetraazabιcyclo[6.6.2]hexadecane Manganese(II) Hexafluorophosphate

Aquo-hydroxy-5,12-dιmethyl-l,5,8.12-tetraazabιcyclo[6.6.2]hexadecane Manganese(UI) Hexafluorophosphate

Dιaquo-4, 10-dimethyl- 1 ,4,7, 10-tetraazabιcyclo[5.5.2]tetradecane Manganese(II) Hexafluorophosphate

Dιaquo-5,12-dιmethyl-l,5,8, 12-tetraazabιcyclo[6.6.2]hexadecane Manganese(II) Tetrafluoroborate Dιaquo-4.10-dιmethyl-1.4,7.10-tetraazabιcyclo[5 5.2]tetradecane Manganese(II) Tetrafluoroborate

Dιchloro-5.12-dιmethyl-l ,5,8, 12-tetraazabιcyclo[6.6.2]hexadecane Manganese(III) Hexafluorophosphate Dιchloro-5, 12-dι-n-butyl-l,5,8, 12-tetraaza- bιcyclo[6.6.2]hexadecane Manganese(II) Dιchloro-5, 12-dιbenzyl-l,5,8,12-tetraazabιcyclo[6.6.2]hexadecane Manganese(II) Dιchloro-5-n-butyl-12-methyl-l,5,8, 12-tetraaza- bιcyclo[6.6.2]hexadecane Manganese(II) Dιchloro-5-n-octyl-12-methyl-l ,5,8,12-tetraaza- bιcyclo[6.6.2]hexadecane Manganese(II) Dιchloro-5-n-butyl-12-methyl-l,5.8.12-tetraaza- bιcyclo[6.6.2]hexadecane Manganese(II) Dιchloro-5, 12-dιmethyl-l,5,8, 12-tetraazabιcyclo[6.6.2]hexadecane Iron(II) Dιchloro-4,10-dιmethyl-l,4,7,10-tetraazabιcyclo[5.5.2]tetradecane Iron(π) Dιchloro-5.12-dιmethyl-1.5,8,12-tetraazabιcyclo[6.6.2]hexadecane Copper(II) Dιchloro-4.10-dimethyl- 1 ,4,7, 10-tetraazabιcyclo[5.5.2]tetradecane Copper(U) Dιchloro-5, 12-dιmethyl-l,5.8,12-tetraazabιcyclo[6.6.2]hexadecane Cobalt(II) Dιchloro-4,10-dιmethyl-l ,4,7,10-tetraazabιcyclo[5.5.2]tetradecane Cobalt(II) Dichloro 5,12-dιmethyl-4-phenyl-l,5,8,12-tetraazabιcyclo[6.6.2]hexadecane

Manganese(IJ) Dιchloro-4,10-dιmethyl-3-phenyl-l,4,7, 10-tetraazabιcyclo[5.5.2]tetradecane Manganese(II) Dιchloro-5, 12-dιmethyl-4,9-dιphenyl-l,5,8,12-tetraazabιcyclo[6.6.2]hexadecane Manganese(II) Dιchloro-4.10-dιmethyl-3 , 8-dιphenyl- 1 ,4,7, 10-tetraazabιcyclo[5.5.2]tetradecane

Manganese(II) Dιchloro-5,12-dιmethyl-2,l l-dιphenyl-l,5,8,12-tetraazabιcyclo[6.6.2]hexadecane Manganese(II) Dιchloro-4,10-dιmethyl-4,9-dιphenyl-l,4,7,10-tetraazabιcyclo[5.5.2]tetradecane Manganese(II) Dιchloro-2,4,5,9,l l,12-hexamethyl-l,5,8,12-tetraazabιcyclo[6.6.2]hexadecane

Manganese(II) Dιchloro-2,3,5,9,10,12-hexamethyl-l,5,8,12-tetraazabιcyclo[6.6.2]hexadecane Manganese(U)

Dιchloro-2,2,4,5,9,9,l l, 12-octamethyl-l,5,8,12-tetraazabιcyclo[6.6.2]hexadecane Manganese(U) Dιchloro-2,2,4,5,9,l l ,l l,12-octamethyl-l,5,8,12-tetraazabιcyclo[6.6.2]hexadecane Manganese(II) Dιchloro-3,3,5,10,10,12-hexamethyl-l,5,8,12-tetraazabιcyclo[6.6.2]hexadecane Manganese(II) Dιchloro-3,5.10,12-tetramethyl-1.5,8,12-tetraazabιcyclo[6.6.2]hexadecane

Manganese(II) Dιchloro-3-butyl-5, 10, 12-tπmethyl-l,5.8, 12-tetraazabιcyclo[6.6.2]hexadecane Manganese(U) Dichloro- 1,5, 8, 12-tetraazabιcyclo[6.6.2]hexadecane Manganese(II) Dichloro- 1,4, 7, 10-tetraazabιcyclo[5.5.2]tetradecane Manganese(II) Dichloro- 1 ,5, 8, 12-tetraazabιcyclo[6.6.2]hexadecane Iron(II) Dichloro- 1, 4,7, 10-tetraazabιcyclo[5.5.2]tetradecane Iron(II)

Aquo-chloro-2-(2-hydroxyphenyl)-5,12-dιmethyl,5.8, 12-tetraazabιcyclo[6.6.2]hexadecane Manganese(II)

Aquo-chloro-10-(2-hydroxybenzyl)-4.10-dιmethyl-1.4.7.10-tetraazabιcyclo[5 5.2]tetradecane

Manganese(II) Chloro-2-(2-hydroxybenzyl)-5-methyl,5,8.12-tetraazabιcyclo[6.6.2]hexadecane Manganese(II) Chloro-10-(2-hydroxybenzyl)-4-methyl-l ,4,7,10-tetraazabιcyclo[5.5.2]tetradecane Manganese(II) Chloro-5-methyl-12-(2-pιcolyl)-l ,5,8, 12-tetraazabιcyclo[6.6.2]hexadecane Manganese(II) Chloride Chloro-4-methyl-10-(2-pιcolyl)-l,4,7,10-tetraazabιcyclo[5.5.2]tetradecane Manganese(II) Chloride Dιchloro-5-(2-sulfato)dodecyl-12-methyl-l,5,8,12-terraazabιcyclo[6.6.2]hexadecane Manganese(UI) Aquo-Chloro-5-(2-sulfato)dodecyl-12-methyl-l,5,8, 12-tetraazabιcyclo[6.6.2]hexadecane Manganese(II)

Aquo-Chloro-5-(3-sulfonopropyl)-12-methyl-l,5.8, 12-tetraazabιcyclo[6.6.2]hexadecane

Manganese(U) Dιchloro-5-(Tπmethylammomopropyl)dodecyl-12-methyl-l,5,8,12-tetraazabιcyclo[6.6.2]hexadecane Manganese(IH) Chloπde Dιchloro-5, 12-dιmethyl-l,4,7,10,13-pentaazabιcyclo[8.5.2]heptadecane Manganese(U) Dichloro- 14,20-dιmethyl- 1,10,14,20-tetraazatπyclo[8.6.6]docosa-3 (8),4,6-tπene

Manganese(II) Dιchloro-4,l l-dιmethyl-l,4,7,l l-tetraazabιcyclo[6.5.2]pentadecane Manganese(II) Dιchloro-5,12-dιmethyl-l,5,8,12-tetraazabιcyclo[7.6.2]heptadecane Manganese(H) Dιchloro-5,13-dιmethyl-l,5,9,13-tetraazabιcyclo[7.7.2]heptadecane Manganese(II)

Dιchloro-3,10-bιs(butylcarboxy)-5,12-dιmethyl-l ,5,8.12-tetraazabιcyclo[6.6.2]hexadecane

Manganese(H) Dιaquo-3,10-dιcarboxy-5,12-dιmethyl-l ,5,8,12-tetraazabιcyclo[6.6.2]hexadecane Manganese(II) Chloro-20-methyl-l ,9,20,24,25-pentaaza-tetracyclo[7.7.7 l^ . l ¹ l >^.]pentacosa-

3,5.7(24), 1 l,13,15(25)-hexaene manganese(II) Hexafluorophosphate Tπfluoromethanesulfono-20-methyl- 1, 9,20,24, 25-pentaaza-tetracyclo[7.7.7.13-^.1 ^_'^ pentacosa- 3.5,7(24),1 1.13, 15(25)-hexaene Manganese(II) Tπfluoromethanesulfonate Tπfluoromethanesulfono-20-methyl-l ,9,20,24,25-pentaaza-tetracyclo[7.7.7.1^'⁷. l ^>^.]pentacosa- 3,5,7(24), 1 l,13,15(25)-hexaene Iron(II) Tπfluoromethanesulfonate Chloro-5, 12,17-tπmethyl-l ,5,8, 12, 17-pentaazabιcyclo[6.6.5]nonadecane Manganese(II)

Hexafluorophosphate Chloro-4, 10, 15-tπmethyl-l ,4,7, 10, 15-pentaazabιcyclo[5.5.5]heptadecane Manganese(II) Hexafluorophosphate

Chloro-5,12,17-tπmethyl-l ,5,8,12,17-pentaazabιcyclo[6.6.5]nonadecane Manganese(II) Chloride Chloro-4, 10,15-tπmethyl- 1 ,4, 7, 10,15-pentaazabιcyclo[5.5.5]heptadecane Manganese(II) Chloride Dichloro 5,12,15.16-tetramethyl-1.5,8.12-tetraazabιcyclo[6.6.2]hexadecane Manganese(II) Chloro 5-methyl-12-(2'-oxybenzyl)-l,5,8,12-tetraazabιcyclo[6.6.2]hexadecane Manganese(II) Preferred complexes useful as transition-metal bleach catalysts more generally include not only monometallic, mononuclear kinds such as those illustrated heremabove but also bimetallic, tπmetalhc or cluster kinds. Monometallic, mononuclear complexes are preferred. As defined herein, a monometallic transition-metal bleach catalyst contains only one transition metal atom per mole of complex. A monometallic, mononuclear complex is one m which any donor atoms of the essential macrocyclic ligand are bonded to the same transition metal atom, that is, the essential ligand does not "bπdge" across two or more transition-metal atoms.

Further examples of manganese transition metal complexes are the manganese(III) and manganese(rV) complexes having the general formula:

wherein X is independently a coordinating or bridging species non-limiting examples of which are H₂0, θX , O^2", ^"OH, H0₂ ^", SH^", S^2", >SO, Cl^", SCN^", N₃\ N^3", RS0₃ ^", RCOO^", NH₂ ^", and NR,, wherein R is H alkyl, aryl, each of which is optionally substituted, and R'COO, wherein R¹ is an alkyl, aryl unit, each of which may be optionally substituted; L is a ligand which is an organic molecule containing a number of nitrogen atoms which co- ordmate via all or some of said nitrogen atoms to the manganese centers; z denotes the charge of the complex and is an integer which can have a positive or negative value, Y is a monovalent or multivalent counter-ion, which provides charge neutrality, which dependent upon the charge z of the complex: and q is z/Y

Prefered of these manganese complexes are those wherein said coordinating or bridging group X is either CH₃COO , O^" , and mixtures thereof, preferably when said manganese atom is m the (IV) oxidation state and X is O² . Ligands which are preferred are those which contain at least three nitrogen atoms and which coordinate via three nitrogen atoms to one of the manganese centers and are preferably of a macrocyclic nature. Preferred ligands have the formula

-[NR- CRWq js-

wherein t is an integer having the value 2 or 3; s is an integer having the value 3 or 4, q is an integer having the value 0 or 1 , R¹ and R² are each independently selected from hydrogen, alkyl, aryl, each of which can be optionally substituted; R³ is independently selected from hydrogen, alkyl. aryl, each of which can be optionally substituted. Non-limitmg examples of preferred ligands are l,4,7-tπmethyl-l ,4,7-tπazacyclononane

(Me₃-TACN), and l,2,4,7-tetramethyl-l,4,7-tnazacyclononane (Me₄-TACN).

The selection of the counter ion Y for establishing charge neutrality is not critical for the activity of the complex. Non-hmitmg examples of said counter ions are chloride, sulphate, nitrate, methylsulphate, surfactant-ions, such as long chain alkylsulphates, alkylsulphonates, alkylbenzenesulphonates. tosylate, trifluoromethylsulphonate, perchlorate, BPhu , PF₆ , and mixtures thereof.

Examples of manganese complexes of this type include:

I) [(Me₃-TACN)Mn^,v(μ-0)₃Mn^IV(Me₃-TACN)]²⁺(PF₆ ^")2;

II) [(Me₄-TACN)Mn^IV(μ-0)₃Mn^IV(Me₄-TACN)]²"(PF₆ ^")₂ ; 111) [(Me₃-TACN)Mn^πι(μ-0)(μ-OAc)₂Mn^ιπ(Me₃-TACN)]²⁺(PF₆ )₂;

IV) [(Me₄-TACN)Mn^ιπ(μ-0)(μ-OAc)₂Mn^III(Me₄-TACN)]²⁺(PF₆ ^")₂; Further manganese complex catalysts are the mononuclear complexes having the formula:

[LMn^IV(OR)₃] Y wherein manganese, Mn, is in the +4 oxidation state; R is C C₂₀ radical selected from the group consisting of alkyl, cycloalkyl, aryl, benzyl, and radical combinations thereof; at least two R radicals may also be connected to one another so as to form a bridging unit between two oxygens that coordinate with the manganese. L is a ligand selected from a C₃-C₆₀ radical having at least 3 nitrogen atoms coordinating with the manganese; and Y is an oxidatively-stable counteπon dependent upon the charge of the complex.

Non-limiting examples of preferred complexes are those wherein L is 1.4,7-tπmethyl- 1.4.7-tπazacyclononane. and 2 methyl-l ,4,7-tπmethyl-l,4,7-tπazacyclononane. and R is Ci alkyl Further examples of mononuclear manganese complex catalysts which are capable of bleaching in the absence of a source of hydrogen peroxide or other peroxygen bleaching agent include those having the formula.

[LMnX_p]^zY_q wherein manganese can be in any of the II, III, or IV oxidation sates, each X independently represents a coordinating species with the exception of RO , such as Cf . Br . I^", F^",

NCS^", N₃\ I₃\ NH₃, RCOO^", RSO₃ ^", RS0 ^", m which R is alkyl or aryl wherein each can be optionally substituted, OH , 0₂ ² , HO_: , H₂0, SH, CN , OCN , S₄ ² , and mixtures thereof; p is an integer from 1 to 3; z denotes the charge of the complex and is an integer which can be positive, zero, or negative; Y is a counter-ion the selection of which dependent upon the charge z of the complex, q = z/Y; and L is a ligand having the formula:

-[NR³ (CR'R²)^

wherein t is 2; s is 3; R¹, R² and R³ are each independently selected from hydrogen, C C₆ alkyl, aryl, each of which can be optionally substituted. METHOD OF USE

The present invention further relates to a method for using the catalysts of the present invention to bleach and/or clean fabric without the requirement of a peroxygen source of peroxygen.

The present invention, therefore, relates to a method for bleaching soils and stains on fabπc in the absence of a bleaching agent, said method compπsmg the step of contacting fabπc in need of cleaning with an aqueous or non-aqueous solution containing a composition which is substantially free of a peroxygen source, comprising: a) a catalytically effective amount of a transition-metal bleach catalyst which is a complex of a transition-metal and a cross-bridged macropolycyclic ligand; and b) the balance carriers, fillers, and other adjunct ingredients; provided the concentration of said transition metal bleach catalyst in the solution is at least about 0.01 ppb and said composition is substantially free of any organic or inorganic peroxygen compounds..

Preferably the solution which comprises the transition-metal bleach catalyst has a solution concentration of catalyst of from about 1 ppb, more preferably from about 10 ppb, yet more preferably from about 100 ppb. For example, 100 ppb (parts per billion) is a solution which comprises 0.00001%o by weight, of a catalyst. As defined herein above, solutions which comprises less than 0.001%> of a source of peroxygen are solutions which are "substantially free" of any organic or inorganic peroxygen compounds. Methods directed entirely to large scale bleaching per se, for example, an industrial or manufacturing process, may utilized a higher concentration of catalyst, for example, 1 ppm or higher m order to reduce the contact time of the fabπc with the catalyst containing solution

ADJUNCT INGREDIENTS The bleaching, pre-soak, pre-treatment, laundry or automatic diswashing, or hard surface cleaning compositions of the present invention, whether granular, solid (bar), gel, or liquid may further comprise one or more carriers and adjunct ingredients.

Compositions according to the present invention may comprise: a) a catalytically effective amount of a transition-metal bleach catalyst which is a complex of a transition-metal and a cross-bridged macropolycyclic ligand; and b) optionally from about 0.001% to about 90%> by weight, of one or more dye fixing agents; c) optionally from about 0.01% to about 50% by weight, of one or more cellulose reactive dye fixing agents; d) optionally from about 0.01% to about 15% by weight, of a chlorine scavenger, e) optionally about 0.005%) to about 1% by weight, of one or more crystal growth inhibitors; f) optionally from about 0.01% to about 20% by weight, of a fabric abrasion reducing polymer; g) optionally from about 1% to about 12% by weight, of one or more liquid carriers, h) optionally from about 0.001% to about 1% by weight, of an enzyme;

I) optionally from about 0.01% to about 8% by weight, of a polyolefm emulsion or suspension; j) optionally from about 0.01 % to about 0.2% by weight, of a stabilizer; k) optionally from about 1% to about 80% by weight, of a fabric softening active; 1) optionally less than about 15% by weight, of a principal solvent; and m) from about 0.01%, preferably from about 0.1%. to about 60%, preferably to about 30% by weight, one or more surfactants, said surfactants selected from the group consisting of aniomc, catiomc, nonionic, ampholytic, zwitteπomc surfactants, and mixtures thereof.

Surfactants

The bleaching, pre-soak, pre-treatment, and laundry detergent compositions of the present invention may comprise at least about 0.01% by weight, preferably from about 0.1% to about 60%, preferably to about 30% by weight, of a detersive surfactant system, said system is comprised of one or more category of surfactants depending upon the embodiment, said categories of surfactants are selected from the group consisting of aniomc, catiomc, nonionic, zwitteπonic, ampholytic surfactants, and mixtures thereof. Within each category of surfactant, more than one type of surfactant of surfactant can be selected. For example, preferably the solid (i.e. granular) and viscous semi-solid (i.e. gelatinous, pastes, etc.) systems of the present invention, surfactant is preferably present to the extent of from about 0.1% to 60 %, preferably to about 30%) by weight of the composition.

Nonhmiting examples of surfactants useful herein include: a) C_π-Ci₈ alkyl benzene sulfonates (LAS); b) C|o-C₂₀ primary, branched-cham and random alkyl sulfates (AS); c) Cio-Cis secondary (2,3) alkyl sulfates having the formula:

OSO₃ ^" M⁺ OSO₃ ^" iv

CH₃(CH₂)χ(CH)CH3 or CH₃(CH₂)y(CH)CH2Cri3 wherein x and (y + 1) are integers of at least about 7, preferably at least about 9; said surfactants disclosed in U.S. 3,234,258 Morris, issued February 8, 1966; U.S. 5,075,041 Lutz, issued December 24, 1991; U.S. 5,349,101 Lutz et al., issued September 20, 1994; and U.S. 5,389,277 Pπeto, issued February 14. 1995 each incorporated herein by reference; d) C₁₀-Cιg alkyl alkoxy sulfates (AE_XS) wherein preferably x is from 1-7; e) Cio-Cig alkyl alkoxy carboxylates preferably comprising 1-5 ethoxy units; f) C₁₂-C₁₈ alkyl ethoxylates, C₆-C_I2 alkyl phenol alkoxylates wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units, Cι -C₎₈ alcohol and C₆-Cι₂ alkyl phenol condensates with ethylene oxide/propylene oxide block polymers inter alia Pluromc^® ex BASF which are disclosed m U.S. 3,929,678 Laughhn et al., issued December 30, 1975, incorporated herein by reference; g) Alkylpolysacchaπdes as disclosed in U S 4,565,647 Llenado, issued January 26, 1986, incorporated herein by reference, h) Polyhydroxy fatty acid amides having the formula-

O R8 R7— C-N-Q wherein R' is C5-C31 alkyl; R° is selected from the group consisting of hydrogen, C1 -C4 alkyl, C 1 -C4 hydroxyalkyl, Q is a polyhydroxyalkyl moiety having a linear alkyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof; preferred alkoxy is ethoxy or propoxy, and mixtures thereof, preferred Q is derived from a reducing sugar m a reductive animation reaction, more preferably Q is a glycityl moiety; Q is more preferably selected from the group consisting of -CH₂(CHOH)_nCH₂OH, -CH(CH₂OH)(CHOH)_n. ι CH₂OH, -CH₂(CHOH)2-(CHOR')(CHOH)CH2θH, and alkoxylated derivatives thereof, wherein n is an integer from 3 to 5, inclusive, and R' is hydrogen or a cyclic or aliphatic monosacchaπde, which are described in U.S. 5,489,393 Connor et al., issued February 6, 1996. and U S. 5,45,982 Murch et al., issued October 3, 1995, both incorporated herein by reference The bleaching, pre-soak, pre-treatment, and laundry detergent compositions of the present invention can also comprise from about 0.001% to about 100% of one or more (preferably a mixture of two or more) mid-cham branched surfactants, preferably mid-cham branched alkyl alkoxy alcohols having the formula.

R R¹ R²

I I I

CH₃CH₂(CH₂)_wCH(CH₂)_xCH(CH₂)_yCH(CH₂)_z(EO PO)_mOH mid-chain branched alkyl sulfates having the formula:

R R¹ R²

I I I

CH₃CH₂(CH₂)_wCH(CH₂)_xCH(CH₂)_yCH(CH₂)_zOS0₃M and mid-cham branched alkyl alkoxy sulfates having the formula:

R R¹ R²

I I I

CH₃CH₂(CH₂)_wCH(CH₂)χCH(CH₂)_yCH(CH₂)₂(EO/PO)_rnOS0₃M wherein the total number of carbon atoms in the branched pπmary alkyl moiety of these formulae (including the R, R , and R^ branching, but not including the carbon atoms which comprise any EO/PO alkoxy moiety) is from 14 to 20, and wherein further for this surfactant mixture the average total number of carbon atoms in the branched pπmary alkyl moieties having the above formula is withm the range of greater than 14.5 to about 17.5 (preferably from about 15 to about 17); R, R¹, and R^ are each independently selected from hydrogen, C1 -C3 alkyl, and mixtures thereof, preferably methyl: provided R, R¹. and R- are not all hydrogen and, when z is 1. at least OΓ R ' is not hydrogen M is a water soluble cation and may comprises more than one type of cation, for example, a mixture of sodium and potassium The index v is an integer from 0 to 13, x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer of at least 1 , provided w + x + y + z is from 8 to 14 EO and PO represent ethyleneoxy units and propyleneoxy units having the formula:

CH₃ CH₃

I I

— CHCH₂0 or — CH₂CHO respectively, however, other alkoxy units inter alia 1 ,3-propyleneoxy, butoxy, and mixtures thereof are suitable as alkoxy units appended to the mid-cham branched alkyl moieties. The mid-chain branched surfactants are preferably mixtures which comprise a surfactant system. Therefore, when the surfactant system comprises an alkoxylated surfactant, the index m indicates the average degree of alkoxylation within the mixture of surfactants As such, the index m is at least about 0.01, preferably within the range of from about 0 1, more preferably from about 0.5, most preferably from about 1 to about 30, preferably to about 10, more preferably to about 5. When considering a mid-cham branched surfactant system which comprises only alkoxylated surfactants, the value of the index m represents a distπbution of the average degree of alkoxylation corresponding to m, or it may be a single specific chain with alkoxylation (e.g., ethoxylation and/or propoxylation) of exactly the number of units corresponding to m

The preferred mid-chain branched surfactants of the present invention which are suitable for use in the surfactant systems of the present invention have the formula:

CH₃

I

CH₃(CH₂)_aCH(CH₂)_bCH₂(EO/PO)_mOS0₃M or the formula:

CH₃ CH₃

I I

CH₃(CH₂)_dCH(CH₂)_eCHCH₂(EO/PO)_rnOS0₃M wherein a, b, d, and e are integers such that a + b is from 10 to 16 and d + e is from 8 to 14; M is selected from sodium, potassium, magnesium, ammonium and substituted ammonium, and mixtures thereof.

The surfactant systems of the present invention which comprise mid-cham branched surfactants are preferably formulated in two embodiments. A first preferred embodiment comprises mid-cham branched surfactants which are formed from a feedstock which compπses 25%o or less of mid-chain branched alkyl units. Therefore, prior to admixture with any other conventional surfactants, the mid-cham branched surfactant component will comprise 25% or less of surfactant molecules which are non-linear surfactants.

A second preferred embodiment comprises mid-cham branched surfactants which are formed from a feedstock which comprises from about 25% to about 70% of mid-cham branched alkyl units. Therefore, prior to admixture with any other conventional surfactants, the mid-chain branched surfactant component will comprise from about 25%> to about 10% surfactant molecules which are non-linear surfactants.

The surfactant systems of the laundry detergent compositions of the present invention can also comprise from about 0 001%, preferably from about 1%, more preferably from about 5%. most preferably from about 10% to about 100%, preferably to about 60%, more preferably to about 30% by weight, of the surfactant system, of one or more (preferably a mixture of two or more) mid-cham branched alkyl arylsulfonate surfactants, preferably surfactants wherein the aryl unit is a benzene πng having the formula'

wherein L is an acyclic hydrocarbyl moiety comprising from 6 to 18 carbon atoms; R¹, R², and R³ are each independently hydrogen or C C₃ alkyl, provided R¹ and R² are not attached at the terminus of the L unit; M is a water soluble cation having charge q wherein a and b are taken together to satisfy charge neutrality. Builders

The compositions of the present invention, especially when compπsing surfactants, preferably comprise one or more detergent builders or builder systems. When present, the compositions will typically comprise at least about 1% builder, preferably from about 5%, more preferably from about 10% to about 80%o, preferably to about 50%, more preferably to about 30%) by weight, of detergent builder.

The level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1%) builder. Formulations typically comprise from about 5% to about 50%, more typically about 5% to about 30%), by weight, of detergent builder. Granular formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, of the detergent builder Lower or higher levels of builder, however, are not meant to be excluded.

Inorganic or P-contaimng detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tnpolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosihcates. However, non-phosphate builders are required in some locales. Importantly, the compositions herein function surprisingly well even in the presence of the so-called "weak" builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt" situation that may occur with zeolite or layered silicate builders.

Examples of silicate builders are the alkali metal silicates described in U.S. 4,664.839 Rieck, issued May 12, 1987. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").

Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.

Alummosilicate builders are useful in the present invention. Examples of suitable alummosilicate builders are described in U.S. 4,274,975 Corkhill et al. included herein by reference. Alummosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Alummosilicate builders include those having the empirical formula:

[M_z(zAlO₂)_y]-xH₂O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264. Preferred synthetic crystalline alummosilicate ion exchange mateπals useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X.

Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide vaπety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized m salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.

Suitable are disclosed m U.S. 3,128,287 Berg, issued Apnl 7, 1964, U.S. 3,635,830 Lambert et al., issued January 18, 1972, U.S. 4,663,071 Bush et al., issued May 5, 1987, U.S. 3,923,679 Rapko, issued December 2, 1975; U S. 4,158,635 Crutchfield et al., issued June 19, 1979; U.S 4.120,874 Crutchfield et al., issued October 17, 1978, U S. 4,566,984, Bush, issued January 28, 1986, U S 4.144,226, Crutchfield et al , issued March 13, 1979 and in U.S. 3.308,067, Diehl, issued March 7, 1967. Diehl U S Patent 3.723,322, and U.S. 4,102,903 Crutchfield et al . issued July 25, 1978 and further U.S. Patents 3,159,581. 3,213,030: 3,422,021, 3,400,148 and 3,422,137.

Citrate builders, e.g , citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradabihty. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccmates are also especially useful m such compositions and combinations. Dispersants

A description of other suitable polyalkyleneimme dispersants which may be optionally combined with the bleach stable dispersants of the present invention can be found in U.S 4,597,898 Vander Meer, issued July 1 , 1986, European Patent Application 1 1 1 ,965 Oh and Gossehnk, published June 27, 1984: European Patent Application 1 1 1,984 Gossehnk, published June 27, 1984, European Patent Application 1 12,592 Gossehnk, published July 4, 1984; U S. 4,548,744 Connor, issued October 22, 1985: and U S. 5.565,145 Watson et al., issued October 15, 1996; all of which are included herein by reference. However, any suitable clay/soil dispersant or anti-redepostion agent can be used m the laundry compositions of the present invention. In addition, polymeric dispersing agents which include polymeric polycarboxylates and polyethylene glycols, are suitable for use m the present invention. Polymenc polycarboxylate materials can be prepared by polymerizing or copolymeπzing suitable unsaturated monomers, preferably m their acid form. Unsaturated monomeπc 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, citracomc acid and methylenemalonic acid The presence m the polymeric polycarboxylates herein or monomeπc segments, containing no carboxylate radicals such as vmylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40%) by weight.

Particularly suitable polymeric polycarboxylates can be deπved from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymeπzed acrylic acid. The average molecular weight of such polymers m the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000 Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type m detergent compositions has been disclosed, for example, m Diehl, U.S Patent 3,308,067, issued march 7, 1967.

Acryhc/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form preferably ranges from about 2,000, preferably from about 5,000, more preferably from about 7,000 to 100,000, more preferably to 75,000, most preferably to 65,000 The ratio of acrylate to maleate segments in such copolymers will generally range from about 30' 1 to about 1.1, more preferably from about 10: 1 to 2' 1 Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts Soluble acrylate/maleate copolymers of this type are known materials which are described m European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also describes such polymers compπsmg hydro xypropylacrylate. Still other useful dispersing agents include the maleic/acryhc/vinyl alcohol teφolymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 teφolymer of acryhc/maleic/vinyl alcohol

Another polymeric material which can be included is polyethylene glycol (PEG). PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent. Typical molecular weight ranges for these puφoses range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.

Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders. Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of about 10,000. Soil Release Agents

The compositions according to the present invention may optionally compπse one or more soil release agents. If utilized, soil release agents will generally compπse from about 0.01%), preferably from about 0.1%, more preferably from about 0.2%> to about 10%, preferably to about 5%, more preferably to about 3% by weight, of the composition. Polymenc soil release agents are characteπzed by having both hydrophilic segments, to hydrophilize the surface of hydiophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of the laundry cycle and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occuπng subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures. The following, all included herein by reference, describe soil release polymers suitable for use in the present invention. U.S. 5,728,671 Rohrbaugh et al , issued March 17, 1998; U.S 5.691.298 Gossehnk et al , issued November 25, 1997; U.S. 5,599,782 Pan et al., issued February 4, 1997; U.S 5,415,807 Gossehnk et al.. issued May 16, 1995; U.S. 5,182,043 Morrall et al , issued January 26, 1993; U.S. 4,956,447 Gossehnk et al, issued September 11, 1990; U.S. 4,976,879 Maldonado et al issued December 11, 1990; U S. 4,968,451 Scheibel et al . issued November 6, 1990; U S. 4.925,577 Borcher, Sr. et al , issued May 15. 1990; U S 4,861,512 Gossehnk, issued August 29, 1989, U S 4,877,896 Maldonado et al , issued October 31 , 1989; U S. 4,771 ,730 Gossehnk et al , issued October 27, 1987; U.S. 71 1,730 Gossehnk et al , issued December 8, 1987; U.S. 4,721,580 Gossehnk issued January 26, 1988; U.S. 4,000,093 Nicol et al , issued December 28, 1976; U.S 3,959,230 Hayes, issued May 25, 1976; U.S. 3,893,929 Basadur, issued July 8, 1975; and European Patent Application 0 219 048, published Apπl 22, 1987 by Kud et /

Further suitable soil release agents are described in U.S. 4,201,824 Voilland et al ; U.S. 4,240,918 Lagasse et al ; U.S. 4,525,524 Tung et al ; U.S. 4,579,681 Ruppert et al , U.S 4,220,918, U.S. 4,787,989; EP 279,134 A, 1988 to Rhone-Poulenc Chemie; EP 457,205 A to BASF (1991); and DE 2,335,044 to Unilever N.V., 1974; all mcoφorated herein by reference. Enzymes

The detergent and cleaning compositions herein may also optionally contain one or more types of detergent enzymes. Such enzymes can include other proteases, amylases, cellulases and hpases. Such matenals are known m the art and are commercially available under such trademarks as . They may be incoφorated into the non-aqueous liquid detergent compositions herein in the form of suspensions, "marumes" or "prills". Another suitable type of enzyme compnses those in the form of slurries of enzymes in nonionic surfactants, e.g., the enzymes marketed by Novo Nordisk under the tradename "SL" or the microencapsulated enzymes marketed by Novo Nordisk under the tradename "LDP." Suitable enzymes and levels of use are described in U.S. Pat. No. 5,576,282, 5,705,464 and 5,710,115.

Enzymes added to the compositions herein in the form of conventional enzyme prills are especially preferred for use herein. Such prills will generally range in size from about 100 to 1,000 microns, more preferably from about 200 to 800 microns and will be suspended throughout the non-aqueous liquid phase of the composition. Prills in the compositions of the present invention have been found, in compaπson with other enzyme forms, to exhibit especially desirable enzyme stability in terms of retention of enzymatic activity over time. Thus, compositions which utilize enzyme prills need not contain conventional enzyme stabilizing such as must frequently be used when enzymes are mcoφorated into aqueous liquid detergents.

However, enzymes added to the compositions herein may be in the form of granulates, preferably T-granulates. "Detersive enzyme", as used herein, means any enzyme having a cleaning, stam removing or otherwise beneficial effect m a laundry, hard surface cleaning or personal care detergent composition. Preferred detersive enzymes are hydrolases such as proteases, amylases and hpases Preferred enzymes for laundry puφoses include, but are not limited to, proteases, cellulases, hpases and peroxidases. Highly preferred for automatic dishwashing are amylases and/or proteases, including both current commercially available types and improved types which, though more and more bleach compatible though successive improvements, have a remaining degree of bleach deactivation susceptibility

Examples of suitable enzymes include, but are not limited to. hemicellulases, peroxidases, proteases, cellulases, xylanases, hpases, phosphohpases, esterases, cutmases, pectinases. keratanases, reductases, oxidases, phenoloxidases, hpoxygenases, hgmnases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabmosidases, hyaluronidase, chondroitmase, laccase, and known amylases. or mixtures thereof.

Examples of such suitable enzymes are disclosed in U.S. Patent Nos. 5,705,464, 5,710,1 15, 5,576,282, 5.728,671 and 5,707,950 The cellulases useful m the present invention include both bacterial or fungal cellulases.

Preferably, they will have a pH optimum of between 5 and 12 and a specific activity above 50 CEVU/mg (Cellulose Viscosity Unit). Suitable cellulases are disclosed in U.S. Patent 4,435,307, J61078384 and WO96/02653 which discloses fungal cellulase produced respectively from Humicola insolens, Tnchoderma, Thielavia and Sporotπchum. EP 739 982 describes cellulases isolated from novel Bacillus species. Suitable cellulases are also disclosed in GB-A-2.075.028, GB-A-2.095.275; DE-OS-2.247.832 and W095/26398.

Examples of such cellulases are cellulases produced by a strain of Humicola msolens (Humicola gπsea var. thermoidea), particularly the Humicola strain DSM 1800. Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 ammo acids; and a ~43kD endoglucanase derived from Humicola insolens, DSM 1800, exhibiting cellulase activity; a preferred endoglucanase component has the ammo acid sequence disclosed in WO 91/17243. Also suitable cellulases are the EGIB cellulases from Tnchoderma longibrachiatum described in WO94/21801 to Genencor. Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described m European patent application No. 91202879.2, filed November 6. 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A S) are especially useful. See also WO91/17244 and WO91/21801. Other suitable cellulases for fabric care and/or cleaning properties are described in WO96/34092, W096/17994 and W095/24471. Cellulases, when present, are normally mcoφorated m the cleaning composition at levels from 0.0001% to 2% of pure enzyme by weight of the cleaning composition.

Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc and with a phenolic substrate as bleach enhancing molecule. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes are known m the art, and include, for example, horseradish peroxidase, hgnmase and haloperoxidase such as chloro- and bromo-peroxidase. Suitable peroxidases and peroxidase-containmg detergent compositions are disclosed, for example, m U.S. Patent Nos. 5,705,464, 5,710, 1 15, 5,576,282, 5,728,671 and 5,707,950, PCT International Application WO 89/099813, WO89/09813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991 and EP No. 96870013.8, filed February 20, 1996. Also suitable is the laccase enzyme.

Enhancers are generally comprised at a level of from 0.1%) to 5% by weight of total composition. Preferred enhancers are substitued phenthiazme and phenoxasme 10- Phenothiazinepropiomcacid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10- phenoxazmepropiomc acid (POP) and 10-methylphenoxazme (descπbed m WO 94/12621) and substitued syπngates (C3-C5 substitued alkyl synngates) and phenols. Sodium percarbonate or perborate are preferred sources of hydrogen peroxide. Said peroxidases are normally mcoφorated in the cleaning composition at levels from 0.0001% to 2% of pure enzyme by weight of the cleaning composition.

Enzymatic systems may be used as bleaching agents. The hydrogen peroxide may also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or during the washing and/or rinsing process. Such enzymatic systems are disclosed in EP Patent Application 91202655.6 filed October 9, 1991.

Other preferred enzymes that can be included in the cleaning compositions of the present invention include hpases. Suitable hpase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeπ ATCC 19.154, as disclosed in British Patent 1,372,034. Suitable hpases include those which show a positive immunological cross-reaction with the antibody of the hpase, produced by the microorganism Pseudomonas fluorescent LAM 1057 This hpase is available from Amano Pharmaceutical Co. Ltd , Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter referred to as "Amano- P" Other suitable commercial hpases include Amano-CES, hpases ex Chromobacter viscosum, e.g Chromobacter viscosum var lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan, Chromobacter viscosum hpases from U S. Biochemical Coφ., U.S.A. and Disoynth Co., The Netherlands, and hpases ex Pseudomonas gladioli Especially suitable hpases are hpases such as Ml ⁿ" LιpomaχR (Gist-Brocades) and LipolaseR and Lipolase UltraR(Novo) which have found to be very effective when used in combination with the compositions of the present invention. Also suitable are the hpolytic enzymes described m EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 by Unilever

Also suitable are cutmases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely hpases which do not require mterfacial activation. Addition of cutmases to cleaning compositions have been described in e g. WO-A-88/09367 (Genencor); WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever)

Lipases and/or cutmases, when present, are normally mcoφorated in the cleaning composition at levels from 0.0001% to 2% of pure enzyme by weight of the cleaning composition. In addition to the above referenced lipases, phosphohpases may be mcoφorated into the cleaning compositions of the present invention. Nonhmitmg examples of suitable phosphohpases included- EC 3.1.1.32 Phospholipase Al ; EC 3.1.1 4 Phospholipase A2; EC 3.1.1.5 Lysophohpase; EC 3.1.4.3 Phospholipase C; EC 3.1 4.4. Phospo pase D. Commercially available phosphohpases include LECITASE® from Novo Nordisk A S of Denmark and Phospholipase A2 from Sigma. When phospolipases are included in the compositions of the present invention, it is preferred that amylases are also included. Without desinng to be bound by theory, it is believed that the combined action of the phospholipase and amylase provide substantive stam removal, especially on greasy/oily, starchy and highly colored stains and soils. Preferably, the phospholipase and amylase, when present, are mcoφorated into the compositions of the present invention at a pure enzyme weight ratio between 4500: 1 and 1 :5, more preferably between 50: 1 and 1 : 1.

Suitable proteases are the subtihsms which are obtained from particular strains of B subtilis and B hcheniformis (subtihsin BPN and BPN') One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243.784 to Novo. Proteolytic enzymes also encompass modified bacterial seπne proteases, such as those described in European Patent Application Serial Number 87 303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "Protease B", and m European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bacterial seπne protealytic enzyme which is called "Protease A" herein. Suitable is the protease called herein "Protease C", which is a variant of an alkaline seπne protease from Bacillus in which Lysme replaced arginine at position 27, tyrosme replaced vahne at position 104, seπne replaced asparagme at position 123. and alanine replaced threomne at position 274. Protease C is described m EP 90915958.4, corresponding to WO 91/06637, Published May 16, 1991 Genetically modified variants, particularly of Protease C, are also included herein.

A preferred protease referred to as "Protease D" is a carbonyl hydrolase as described in U.S. Patent No. 5,677,272, and WO95/10591. Also suitable is a carbonyl hydrolase variant of the protease described m WO95/10591, having an ammo acid sequence derived by replacement of a plurality of ammo acid residues replaced m the precursor enzyme corresponding to position +210 in combination with one or more of the following residues : +33, +62, +67, +76, +100, +101, +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218, and +222, where the numbered position corresponds to naturally- occurring subtilism from Bacillus amyloliquefaciens or to equivalent ammo acid residues m other carbonyl hydrolases or subtihsins, such as Bacillus lentus subtilism (co-pending patent application US Serial No. 60/048,550, filed June 04, 1997 and PCT International Application Serial No. PCT/IB98/00853).

Also suitable for the present invention are proteases descnbed in patent applications EP 251 446 and WO 91/06637, protease BLAP® described m WO91/02792 and their vaπants descnbed in WO 95/23221.

See also a high pH protease from Bacillus sp. NCLMB 40338 described in WO 93/18140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are descnbed in WO 92/03529 A to Novo. When desired, a protease having decreased adsoφtion and increased hydrolysis is available as descnbed in WO 95/07791 to Procter & Gamble. A recombmant trypsin-hke protease for detergents suitable herein is descnbed in WO 94/25583 to Novo. Other suitable proteases are descnbed in EP 516 200 by Unilever. Particularly useful proteases are described in PCT publications. WO 95/30010; WO

95/3001 1 ; and WO 95/29979 Suitable proteases are commercially available as ESPERASE®,

ALCALASE®, DURAZYM®, SAVLNASE®, EVERLASE® and KANNASE® all from Novo

Nordisk A/S of Denmark, and as MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® all from Genencor International (formerly Gist-Brocades of The Netherlands)

Such proteolytic enzymes, when present, are incoφorated in the cleaning compositions of the present invention a level of from 0.0001% to 2%, preferably from 0 001% to 0.2%, more preferably from 0.005%o to 0 1% pure enzyme by weight of the composition

Amylases (α and/or β) can be included for removal of carbohydrate-based stains WO94/02597 describes cleaning compositions which mcoφorate mutant amylases. See also W095/ 10603 Other amylases known for use m cleaning compositions include both α- and β- amylases α-Amylases are known in the art and include those disclosed in US Pat. no. 5,003,257, EP 252,666; WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341 ; and British Patent specification no. 1.296,839 (Novo). Other suitable amylases are stability-enhanced amylases described in W094/18314 and WO96/05295, Genencor, and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed m WO 95/10603. Also suitable are amylases described in EP 277 216

Examples of commercial α-amylases products are Purafect Ox Am® from Genencor and

Termamyl®, Ban® ,Fungamyl® and Duramyl®, all available from Novo Nordisk A S Denmark. W095/26397 descπbes other suitable amylases : α-amylases charactensed by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25°

C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas® α-amylase activity assay. Suitable are vanants of the above enzymes, descnbed in W096/23873 (Novo Nordisk). Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostabihty and a higher activity level are described in W095/35382. Such amylolytic enzymes, when present, are mcoφorated in the cleaning compositions of the present invention a level of from 0.0001% to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024%) to 0.048%> pure enzyme by weight of the composition.

The above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Ongm can further be mesophilic or extremophihc (psychrophihc, psychrotrophic, hermophilic, barophihc, alkalophihc, acidophihc, halophihc, etc.). Purified or non-punfied forms of these enzymes may be used. Nowadays, it is common practice to modify wild-type enzymes via protein / genetic engmeeπng techniques in order to optimize their performance efficiency m the laundry detergent and/or fabric care compositions of the invention. For example, the variants may be designed such that the compatibility of the enzyme to commonly encountered ingredients of such compositions is increased. Alternatively, the variant may be designed such that the optimal pH. bleach or chelant stability, catalytic activity and the like, of the enzyme variant is tailored to suit the particular cleaning application.

In particular, attention should be focused on ammo acids sensitive to oxidation in the case of bleach stability and on surface charges for the surfactant compatibility. The isoelectric point of such enzymes may be modified by the substitution of some charged ammo acids, e.g. an increase in isoelectric point may help to improve compatibility with aniomc surfactants. The stability of the enzymes may be further enhanced by the creation of e g. additional salt bridges and enforcing calcium binding sites to increase chelant stability

These optional detersive enzymes, when present, are normally coφorated m the cleaning composition at levels from 0.0001%o to 2% of pure enzyme by weight of the cleaning composition. The enzymes can be added as separate single ingredients (prills, granulates, stabilized liquids, etc... containing one enzyme ) or as mixtures of two or more enzymes ( e.g. cogranulates ).

Other suitable detergent ingredients that can be added are enzyme oxidation scavengers Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyammes.

A range of enzyme materials and means for their mcoφoration into synthetic detergent compositions is also disclosed in WO 9307263 and WO 9307260 to Genencor International, WO

8908694, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in

U.S 4, 101 ,457, and in U.S. 4,507,219. Enzyme materials useful for liquid detergent formulations, and their incoφoration into such formulations, are disclosed m U.S. 4,261,868.

Amylase enzymes are suitable for use in the compositions of the present invention. Amylase enzymes and variants used in the present invention include, but are not limited to, the amylase enzymes descnbed in WO 95/26397 and in WO 96/23873 (Novo). These enzymes are mcoφorated into cleaning compositions at a level of from about 0.0001 ), preferably from about 0.00018%), more preferably from about 0.00024%), most preferably from about 0.05% to about 0.1%), preferably to about 0.060%>, more preferably to about 0.048%) by weight of the cleaning compositions of pure enzyme.

The amylase variants are preferably selected from the group consisting of α-amylase vaπants.

Suitable α-amylase variants for use m the present invention include, but are not limited to the following α-amylases: (i) α-amylase characterized by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by Phadebas® α-amylase activity assay and/or;

(π) α-amylase according to (l) comprising the ammo acid sequence shown in SEQ LO NO. 1 or an α-amylase being at least 80% homologous with the ammo acid sequence shown in SEQ LD No 1 and/or;

(in) α-amylase according to (l) comprising the ammo acid sequence shown in SEQ LD No 2 or an α-amylase being at least 80% homologous with the ammo acid sequence shown m SEQ LD No. 2 and/or; (IV) α-amylase according to (l) compπsmg the following ammo acid sequence N- terminal. Hιs-Hιs-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Tφ-Tyr-Leu-Pro-Asn- Asp (SEQ LD No. 3) or an α-amylase being at least 80%o homologous with the ammo acid sequence shown (SEQ LD No. 3) in the N-termmal and/or;

(v) α-amylase according to (i-iv) wherein the α-amylase is obtainable from an alkalophihc Bacillus species and/or;

(vi) α-amylase according to (v) wherein the amylase is obtainable from any of the strains NCIB 12289, NCLB 12512, NCLB 12513 and DSM 935 and/or;

(vn) α-amylase showing positive lmmunological cross-reactivity with antibodies raised against an α-amylase having an ammo acid sequence corresponding respectively to SEQ LD No. 1 , LD No. 2, or LD No. 3 and/or;

(vin) vanant of a parent α-amylase, wherein the parent α-amylase (1) has one of the ammo acid sequences shown in SEQ LD No. 1, LD No. 2, or LD No. 4, respectively, or (2) displays at least 80%> homology with one or more of said ammo acid sequences, and/or displays lmmunological cross-reactivity with an antibody raised against an α-amylase having one of said ammo acid sequences, and or is encoded by a DNA sequence which hybndizes with the same probe as a DNA sequence encoding an α-amylase having one of said ammo acid sequences, in which variants: (A) at least one ammo acid residue of said parent α-amylase has been deleted; and or (B) at least one ammo acid residue of said parent α-amylase has been replaced by a different ammo acid residue; and or (C) at least one ammo acid residue has been inserted relative to said parent α-amylase; said variant having an α-amylase activity and exhibiting at least one of the following properties relative to said parent α-amylase: increased thermostabihty; increased stability towards oxidation; reduced Ca ion dependency; increased stability and/or α-amylolytic activity at neutral to relatively high pH values; increased α-amylolytic activity at relatively high temperature; and increase or decrease of the isoelectric point (pi) so as to better match the pi value for α-amylase variant to the pH of the medium.

A polypeptide is considered to be X% homologous to the parent amylase if a comparison of the respective ammo acid sequences, performed via algorithms, such as the one described by Lipman and Pearson in Science 227. 1985, p. 1435, reveals an identity of X%

In the context of the present invention, the term "obtainable from" is intended not only to indicate an amylase produced by a Bacillus strain but also an amylase encoded by a DNA sequence isolated from such a Bacillus strain and produced in a host organism transformed with the DNA sequence. Enzyme Stabilizers

Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified m U S 3,600,319, EP 199.405 and EP 200.586 Enzyme stabilization systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp. AC 13 giving proteases, xylanases and cellulases, is described in WO 9401532. The enzymes employed herein can be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes. Suitable enzyme stabilizers and levels of use are described in U.S. Pat. Nos 5,705,464, 5,710,115 and 5,576,282.

The following is a non-hmitmg example of the preparation of a bleach catalyst which effectively bleaches stains m the absence of a source of peroxygen.

EXAMPLE 1 Synthesis of 5,12-dιmethyl-1.5,8.12-tetτaaza-bιcyclo 6.6.2]hexadecane manganese (II) chloride, having the formula:

To a 250 mL, 3 necked round bottom flask, equipped with a thermometer, nitrogen inlet, and magnetic stirrer is added N,N'-bιs(2-amιnoethyl)-l,3-propanedιamme (5.00g, 31.3 mmol) and absolute ethanol (100 mL). The solution is stirred under argon and cooled to 15°C using an ice bath. Aqueous glyoxal (4.78 g., 33 mmol, 40% m water) is added dropwise with stirπng Upon completion of the addition, the solution is concentrated under reduced pressure to yield a clear, colorless oil. The isolated oil has the formula 1.

1 and is obtained in 100% yield (6.0 g).

Cyclic amine 1 (6.0 g) is suspended in acetonitπle (100 mL). Potassium carbonate (25 g) and 1 ,3-propanedιol ditosylate (12.61 g, 32.8 mmol) is added. The solution is stirred vigorously at RT overnight. The reaction is then warmed to 70°C and filtered hot with glass fiber filter paper and vacuum filtration. The resulting solid is washed with acetonitπle (100 mL). The acetonitπle filtrate is concentrated under reduced pressure to yield a light green oil having the formula 2 :

and is obtained m 100% yield (7.0 g).

The tetraamme 2, (7.0 g) is dissolved in acetonitπle (150 mL). Methyl sulfate (2.5 equiv.) is added, the reaction warmed to 65°C and stirred for 9 days. The solvent is removed under reduced pressure to yield a brown oil having the formula 3 :

and is obtained in approximately 85% yield. Distilled water (25 mL) and potassium carbonate (13 8 g) are added to a 250 mL round bottomed flask. Absolute ethanol (75 mL) is added and the resulting biphasic solution is stirred and heated to 60°C with an oil bath. Sodium borohydπde (1.60 g., 42.3 mmol) and 3 (10.0 g., 21 1 mmol) was added to the solution The reaction is stirred at 60°C for 75 minutes The reaction mixture is placed in a separatory funnel and the ethanol layer collected. The solvent is then removed under reduced pressure, the resulting tan solid/oil is dissolved in 5N KOH (5 mL) and extracted with toluene (2 x 50 mL). The toluene is removed under reduced pressure to yield 5.12-dιmethyl-l,5.8,12-tetraaza-bιcyclo[6.6.2]hexadecane having the formula.

4 as an oil, in 95%> yield (5.2 g) after distillation

To a flame dried 12 liter, 3 neck round bottom flask equipped with a heating mantle, stir bar. and oven dried condenser is added anhydrous acetonitπle (5 liters) and yield 5,12-dιmefhyl- l,5,8,12-tetraaza-bιcyclo[6.6.2]hexadecane (484 gm., 1.9 moles). The milky white suspension is placed under a 10 mm vacuum until the suspension boiled and then the reaction vessel flushed with argon. This degassing is performed 7 times. After degassing is complete manganese (II) chloride (228 gm, 1.81 moles) is added. After refluxmg for 4 hours with vigorous stimng, the suspension is immediately filtered through glass filter paper. The solvent is removed from the filtrate under reduced pressure at 45° C to yield a solid. The solid is then suspended in 500 ml toluene, and the supernatant decanted off. This washing is repeated until the supernatant is free of color (typically 7 times with about 7X500 ml of toluene). The solid which remains I dried in vacuo to yield 575 g (84%) of 5,12-dιmethyl-l,5,8,12-tetraaza-bιcyclo[6.6.2]hexadecane magnanese (II) chloride. A second crop of product is obtained by further washing of the solid material and subsequent treatment of the resulting solid in a like manner. Total yield is 636 g (93%). The following are non-limiting examples of Heavy Duty Granular (HDG) laundry detergent compositions according to the present invention. TABLE I weight %

1. 5,12-dιmethyl-l,5,8,12-tetraaza-bιcyclo[6.6.2]hexadecane manganese (II) chlonde.

TABLE ϋ weight %o

The following are non-hmiting examples of Heavy Duty Liquid (HDL) laundry detergent compositions according to the present invention.

TABLE m weight %

TABLE IV

Claims

WHAT IS CLAIMED IS:

1 A bleaching composition comprising

A) a catalytically effective amount of a transition-metal bleach catalyst which is a complex of a transition-metal and a cross-bridged macropolycyclic ligand, and

B) the balance carriers and other adjunct ingredients, provided said composition is substantially free of any organic or inorganic peroxygen compounds

2 A composition according to Claim 1 wherein said transition-metal bleach catalyst comprises l) a transition metal selected from the group consisting of Mn(IL), Mn(ILJ), Mn(LV),

Mn(V), Fe(II), Fe(ffl). Fe(LV), Co(I), Co(II), Co(ffl), Nι(I), Nι(II), Nι(III), Cu(I) Cu(II), Cu(III), Cr(II), Cr(III), Cr(LV), Cr(V), Cr(VI), V(III), V(LV), V(V), Mo(LV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(LI), Ru(II), Ru(III), and Ru(LV), preferably Mn(II), Mn(III), Mn(LV), Fe(II). Fe(III), Fe(LV), Cr(II), Cr(πi), Cr(LV), Cr(V), Cr(VI), and mixtures thereof, and n) a cross-bridged macropolycyclic ligand being coordinated by four or five donor atoms to the same transition metal, said ligand comprising a) an organic macrocycle ring containing four or more donor atoms (preferably at least 3, more preferably at least 4, of these donor atoms are N) separated from each other by covalent linkages of 2 or 3 non-donor atoms, two to five (preferably three to four, more preferably four) ol these donor atoms being coordinated to the same transition metal atom in the complex, b) a cross-bπdged chain which covalently connects at least 2 non-adjacent donor atoms of the organic macrocycle nng, said covalently connected non-adjacent donor atoms being bπdgehead donor atoms which are coordinated to the same transition metal in the complex, and wherein said cross-bridged chain comprises from 2 to 10 atoms (preferably the cross-bndged chain is selected from 2, 3 or 4 non-donor atoms, and 4-6 non-donor atoms with a further donor atom), c) optionally, one or more non-macropolycyc c ligands, preferably selected from the group consisting of H2O, ROH, NR3, RCN, OH^", OOH^", RS^",

RO^", RCOO^", OCN^". SCN^", N3^". CN^", F^", Cl^", Br^", I^", O2^". NO3^", NO2^",

2- 2- 3-

Sθ4~ , SO3^" , PO4 , organic phosphates, organic phosphonates, organic sulfates, organic sulfonates, and aromatic N donors such as pyπdines, pyrazines, pyrazoles, lmidazoles. benzimidazoles, pyπmidmes, tπazoles and thiazoles with R being H, optionally substituted alkyl, optionally substituted aryl

A composition according to either Claim 1 or 2 wherein said organic macrocycle ring comprises at least four donor atoms which are N, said donor atoms separated from each other by covalent linkages of from 2 to 4 non-donor atoms, said donor atoms coordinated to the same transition metal atom

A composition according to any of Claims 1 - 3 wherein said donor atoms in the organic macrocycle ring of the cross-bridged macropolycyclic ligand are selected from the group consisting of nitrogen, oxygen, sulfur, phosphorous, and mixtures thereof.

5 A composition according to any of Claims 1 - 4 comprising a transition-metal bleach catalyst wherein at least four of the donor atoms in the cross-bridged macropolycyclic ligand, form an apical bond angle with the same transition metal of 180+50° and at least one equatorial bond angle of 90±20°.

6 A composition according to any of Claims 1 - 5 which comprises at least 1 ppb of 5,12- dιmethyl-l,5,8,12-tetraaza-bιcyclo[6.6.2]hexadecane manganese(II) chloπde.

7. A composition according to any of Claims 1 - 5 which comprises at least 1 ppb of 5,12- dιethyl-l,5,8,12-tetraaza-bιcyclo[6.6.2]hexadecane manganese(II) chloπde.

8. A liquid laundry, laundry pre-soak, or pre-treatment composition comprising: a) a catalytically effective amount of a transition-metal bleach catalyst which is a complex of a transition-metal and a cross-bπdged macropolycyclic ligand; and b) the balance one or more liquid carriers, provided said composition is substantially free of any organic or inorganic peroxygen compounds.

A composition according to Claim 8 wherein said catalyst comprises:

I) a transition metal is selected from the group consisting of Mn(II), Mn(III),

Mn(LV), Mn(V), Fe(II), Fe(III), Fe(LV), Co(I), Co(II), Co(III), Nι(I), Nι(II), Nι(iπ), Cu(I), Cu(LL), Cu(III), Cr(II), Cr(πi), Cr(LV), Cr(V), Cr(VI), V(ffl), V(LV), V(V), Mo(LV), Mo(V), Mo(VI), W(LV), W(V), W(VI). Pd(II), Ru(II), Ru(ffl), and Ru(LV), and; n) a cross-bridged macropolycyclic ligand, said ligand is selected from the group consisting of: a) a cross-bridged macropolycyclic ligand of formula (I) having denticity of

4 or 5:

(i); b) a cross-bndged macropolycyclic ligand of formula (II) having denticity of 5 or 6:

(II), c) the cross-bridged macropolycyclic ligand of formula (ILL) having denticity of 6 or 7-

(ffl); wherein each E unit represents the moiety having the formula: (CR_n)_a-X-(CR_n)_a. wherein X is selected from the group consisting of oxygen, sulfur, -NR-, phosphorous, or X represents a covalent bond wherein E has the formula: (CR_n)_a-(CR_n)_a' for each E units the sum of a + a' is independently selected from 1 to 5; each G unit is a moiety (CR_n)b; each R unit is independently selected from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl, and heteroaryl, or two or more R units are covalently bonded to form an aromatic, heteroaromatic, cycloalkyl, or heterocycloalkyl ring; each D unit is a donor atom independently selected from the group consisting of nitrogen, oxygen, sulfur, and phosphorous, and at least two atoms which comprise D units are bridgehead donor atoms coordinated to the transition metal; B units are a carbon atom, a D unit, or a cycloalkyl or heterocychc ring; each n is an integer independently selected from 1 and 2, completing the valence of the carbon atoms to which the R units are covalently bonded; each n' is an integer independently selected from 0 and 1, completing the valence of the D donor atoms to which the R moieties are covalently bonded; each n" is an integer independently selected from 0. 1, and 2 completing the valence of the B atoms to which the R moieties are covalently bonded; each a and a' is an integer independently selected from 0 to 5, wherein the sum of all a + a' values in the ligand of formula (I) is within the range of from 8 to 12; the sum of all a -r a' values in the ligand of formula (II) is within the range of from 10 to 15; and the sum of all a + a¹ values m the ligand of formula (ILL) is within the range of from 12 to 18; each b is an integer independently selected from 0 to 9, or in any of the above formulas, one or more of the (CR_n)_D moieties covalently bonded from any D to the B atom is absent as long as at least two (CR_n)^ covalently bond two of the D donor atoms to the B atom in the formula, and the sum of all b indices is within the range of from 2 to 5; and d) optionally, one or more non-macropolycychc ligands.

10. A composition according to either Claim 8 or 9 wherein said catalyst comprises a non- macropolycychc ligand selected from the group consisting of H2O, ROH, NR3, RCN,

OH^", OOH^", RS^", RO^", RCOO^", OCN^", SCN^", N3^", CN^", F^", Cl^", Br^", I^", O2^", NO3^",

2- 2- 3-

NO2 , SO4 , SO3 , PO4 , organic phosphates, organic phosphonates, organic sulfates, organic sulfonates, and aromatic N donors such as pyπdines, pyrazmes, pyrazoles, imidazoles, benzimidazoles, pyπmidines, tnazoles and thiazoles; wherein R is H, alkyl which is optionally substituted, and aryl which is optionally substituted. A method for bleaching soils and stains on fabrics, said method comprising the step of contacting fabric m need of cleaning with an aqueous or non-aqueous solution containing a composition comprising: a) a catalytically effective amount of a transition-metal bleach catalyst which is a complex of a transition-metal and a cross-bridged macropolycyclic ligand; and b) the balance carriers, fillers, and other adjunct ingredients; provided the concentration of said transition metal bleach catalyst in the solution is at least 0.01 ppb and said composition is substantially free of any organic or inorganic peroxygen compounds.