DE60025472T2 - STABILIZED BLEACHING COMPOSITIONS - Google Patents

Description

AREA OF INVENTION

The The present invention relates to stabilized bleach and detergent compositions, which is a catalytically effective amount of a transition metal bleach catalyst, a complex of a transition metal and a cross-linked one Macropolycyclic ligand, and an antioxidant or Reducing agent which serves to stabilize the catalyst, include. The present invention further relates to a method for bleaching / cleaning fabric with a catalytically active Amount of the stabilized transition metal bleach catalyst, the process being essentially free of any organic or inorganic peroxygen compound or precursors of any organic or inorganic peroxygen compound is carried out.

BACKGROUND THE INVENTION

bleaching Substance consists essentially of polluted or stained Substance of a chemical reaction whose purpose is the removal of the Dirt or stain is to suspend. Once upon a time, bleaching involved the substance of a hypochlorite solution suspend. That's why were substances containing sensitive pigments colored were excluded from treatment with bleach. For the benefit of the consumer developed different forms of Bleaching agents, including peroxide bleaching systems, usually a hydrogen peroxide source and a bleach activator. This combination of hydrogen peroxide source and activator plays a crucial role in effective, safe bleaching compositions. An effective example of this peroxide bleaching system uses perborate (Peroxide source) and nonanoyloxybenzenesulfonate (activator).

Around to improve the performance of bleaching agents and bleaching systems too develop that for every kind of colored Fabric, including silk, polyester blends, cotton, nylon, are safe, manufacturers continue to develop peroxide bleach systems as well as new processes for the formation of activated oxygen.

however There is still a need for a stable technology Bleaching system, the substance without required reactive chemicals such as peroxides, peroxide sources and / or mixtures thereof bleaches effectively. The stable bleaching system comprises a transition metal catalyst, not by the instability of the catalyst upon oxidation and / or reduction after formulation loses effectiveness. WO 99/00473 discloses non-aqueous liquid detergents, comprising bleach precursors and / or bleach and a compound that is capable of with the oxygen caused by the decomposition of the bleach precursor and / or Bleaching agent is released, such as a catalyst. WO 98/39045 relates to laundry or cleaning compositions, the bleach activator and / or organic percarboxylic acid, a Catalyst and an oxygen bleach include. WO 00/29537 discloses compositions comprising bleach catalyst, wherein the compositions are substantially free of any organic or inorganic peroxygen compounds.

SUMMARY THE INVENTION

The present invention the above requirements insofar as found out surprising was that bleaching systems containing a transition metal catalyst include and which are able to remove dirt and stains in Absence of a hydrogen peroxide source or other peroxide bleach to bleach successfully against unwanted decomposition of the transition metal catalyst can be stabilized. In other words, it became surprising found that the addition of an effective amount of an antioxidant and / or radical scavengers or a reducing agent completely hydrogen peroxide-free Stabilize bleach system.

• A) eine katalytisch wirksame Menge eines Übergangsmetall-Bleichmittelkatalysators, der ein Komplex eines Übergangsmetalls und eines querverbrückten makropolycyclischen Liganden ist;
• B) eine wirksame Menge eines Stabilisierungsmittels, wobei das Mittel ausgewählt ist aus i) einem oder mehreren Antioxidationsmitteln; ii) einem oder mehreren Reduktionsmitteln; iii) und Mischungen davon; und
• C) zu übrigen Teilen Träger und andere Zusatzbestandteile;

mit der Maßgabe, dass die Zusammensetzung im Wesentlichen frei von jeglichen organischen oder anorganischen Persauerstoffverbindungen ist.A first aspect of the present invention relates to stabilized 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;
• B) an effective amount of a stabilizing agent, said agent being selected from i) one or more antioxidants; ii) one or more reducing agents; iii) and mixtures thereof; and
• C) other parts Carrier and other additional components;

with the proviso that the composition is substantially free of any organic or inorganic peroxygen compounds.

• A) eine katalytisch wirksame Menge eines Übergangsmetall-Bleichmittelkatalysators, der ein Komplex eines Übergangsmetalls und eines querverbrückten makropolycyclischen Liganden ist;
• B) eine wirksame Menge eines Stabilisierungsmittels, wobei das Mittel ausgewählt ist aus i) 0,01 bis 10 Gew.-% an einem oder mehreren Antioxidationsmitteln; ii) 0,001 bis 1 Gew.-% an einem oder mehreren Reduktionsmitteln; iii) und Mischungen davon; und
• C) zu übrigen Teilen Träger und andere Zusatzbestandteile;

mit der Maßgabe, dass die Konzentration des Übergangsmetall-Bleichmittelkatalysators in der wässrigen Lösung mindestens ungefähr 0,01 ppb ist und die Zusammensetzung im Wesentlichen frei von jeglichen organischen oder anorganischen Persauerstoffverbindungen ist.The present invention further relates to a method of cleaning and / or bleaching stains and stains on fabrics, the method comprising the step of contacting the fabric to be cleaned and / or bleached with an aqueous solution containing a composition comprising is substantially free of a peroxide source and 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;
• B) an effective amount of a stabilizing agent, wherein the agent is selected from i) 0.01 to 10% by weight of one or more antioxidants; ii) from 0.001 to 1% by weight of one or more reducing agents; iii) and mixtures thereof; and
• C) other parts Carrier and other additional components;

with the proviso that the concentration of the transition metal bleach catalyst in the aqueous solution is at least about 0.01 ppb and the composition is substantially free of any organic or inorganic peroxygen compounds.

The Compositions and methods of the present invention are to clean / bleach any surface, during stain removal is required, suitable. For example, detergents for hard surfaces and machine dishwashing compositions the bleach catalysts of the present invention in applications, essentially free from any organic or inorganic peroxygen compounds are, insert.

At the By reading the following detailed description and the enclosed claims These and other purposes, features and benefits over those previously used in engineering significantly.

All percentages used here, conditions and proportions are on a weight basis, if nothing else is specified. All temperatures are in degrees Celsius (° C), provided not stated otherwise. All cited documents are, in relevant Parts incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION

The The present invention relates to the surprising discovery that transition metal catalysts, who are able to remove stains and stains in the absence to bleach a peroxide bleach additive, by adding a or more stabilizing agents can. Stabilizing agents for use in the present Invention are present in varying concentrations, dependent from the formulation, inter alia, liquid, solid, gel, and the concentration of the existing transition metal.

absence from peroxide sources

The compositions of the present invention, as well as the processes for cleaning and / or bleaching fabric using the compositions of the present invention, are substantially free of any source of peroxide, such as hydrogen peroxide, peroxyacid, etc. The compositions of the present invention require only those for effective bleaching Presence of an effective amount of the catalyst described below. For the purposes of the present invention, the term "substantially free" is defined to mean that the manufacturer does not require a peroxygen compound or peroxide source in a concentration required for either efficient bleaching without transition metal catalyst or an increase in bleaching efficiency in the presence Therefore, as further described below, effective bleaching of stains can be achieved by simply adding an aqueous or nonaqueous solution of a catalyst as described herein to the stained material Preferably, the substance is in an aqueous solution when contacted with the catalyst It is recognized, however, that due to factors beyond the control of the manufacturer, including sources of product starting materials, undesirable decomposition of one or more In other ingredients, a peroxide source may be unknowingly introduced into the product and / or formed in the product. The composition The present invention does not require a peroxide source, but the presence of small amounts does not affect the performance of the bleaching compositions herein.

Manufacturer can usually a small amount of a hydrogen peroxide source in absorb the compositions to stabilize enzymes, for For example, a small amount of perborate may be added. however This amount of perborate is usually so low that it reduces the bleaching performance of the compositions of the present invention. In cases, in which the manufacturer for the purposes of the present invention are a small amount of an oxidizing agent or another peroxide source added to an adjunct ingredient To stabilize, these compositions are still considered "essentially free "from one Peroxide source defined as defined above when under typical use conditions no additional bleach activity on stains provide. For example, a "substantially free" composition a peroxide source amount, with the proviso that the degree to which the catalyst is effective, essentially the same as in the absence of the peroxide source. For the purposes of the present Invention is any composition that is less than 0.1%, preferably less than 0.01% primary Oxidizing agent, such as a preformed peracid or hydrogen peroxide source, includes, as "im Essentially free ", as further defined above. In addition, every wash liquor, Laundry liquor, Soaking liquor or other fabric or surface cleaning solution, wherein the present catalysts are used and those too less as 0.001% by weight of a peroxide source, preformed or otherwise in situ, herein defined as "substantially free" as above Are defined. In other words, when the catalysts of the present invention for bleaching stains on fabric or otherwise cleaning / bleaching a hard surface or used by dishes and the solution containing the catalyst, a Having a concentration of peroxide source of less than 0.001%, will this solution herein as "im Essentially free "of a peroxide source defined.

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, those in the compositions of the present invention or during the Use according to the methods present invention, which is sufficient to any conditions of comparison or use at least partial oxidation of the material by the composition or the process is to be oxidized. In general, that is material to be oxidized an undesirable substance, among others Food and beverage stains, greasy / oily Stains, body dirt on fabric, but this is not a limitation on the applicability of the invention. Oxidation in the absence of a peroxide source has wide applications, and the present invention is not limited to bleaching and / or Cleaning of fabric limited. For example, machine dishwashing compositions are one embodiment the present invention, in which the bleaching of a stain with a composition and / or a solution that is "substantially free" from a peroxide source is part of the present invention. this applies as well for Cleaning compositions for hard surfaces and solutions, comprising hard surface cleaning compositions, the "im Essentially free "of a peroxide source.

Preferably For example, the compositions of the present invention comprise about 1 ppb (0.0000001 %), more preferably about 100 ppb (0.00001%), more preferably about 500 ppb (0.00005%), more preferably from about 1 ppm (0.0001%) to about 99.9 %, more preferably to about 50%, more preferably up to about 5%, even more preferred until about 500 ppm (0.05%), by weight of the composition, of a transition metal bleach catalyst, as described below.

• i) einen Übergangsmetall, ausgewählt aus der Gruppe, bestehend aus Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I), Cu(II), Cu(III), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), 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), vorzugsweise Mn(II), Mn(III), Mn(IV), Fe(II), Fe(III), Fe(IV), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), und Mischungen davon; und
• ii) einen makropolycyclischen Liganden mit Querbrücken, der von vier oder fünf Donoratomen an dasselbe Übergangsmetall koordiniert wird, wobei der Ligand umfasst:
• a) einen organischen makrocyclischen Ring, enthaltend vier oder mehr Donoratome (vorzugsweise sind mindestens 3, noch bevorzugter mindestens 4 dieser Donoratome N), die voneinander durch kovalente Bindungen aus 2 oder 3 Nichtdonoratomen getrennt sind, wobei zwei bis fünf (vorzugsweise drei bis vier, noch bevorzugter vier) dieser Donoratome an dasselbe Übergangsmetallatom in dem Komplex koordiniert sind;
• b) eine Kette mit Querbrücken, die mindestens 2 nicht benachbarte Donoratome des organischen, makrocyclischen Rings kovalent verbindet, wobei die kovalent verbundenen, nicht benachbarten Donoratome Brückenkopf-Donoratome sind, die an dasselbe Übergangsmetall in dem Komplex koordiniert sind, und worin die Kette mit den Querbrücken 2 bis etwa 10 Atome umfasst (vorzugsweise ist die Kette mit Querbrücken ausgewählt aus 2, 3 oder 4 Nichtdonoratomen und 4–6 Nichtdonoratomen mit einem weiteren Donoratom);
• c) wahlweise einen oder mehrere nicht makropolycyclische Liganden, vorzugsweise ausgewählt aus der Gruppe, bestehend aus H₂O, ROH, NR₃, RCN, OH^–, OOH^–, RS^–, RO^–, RCOO^–, OCN^–, SCN^–, N₃ ^–, CN^–, F^–, Cl^–, Br^–, I^–, O₂ ^–, NO₃ ^–, NO₂ ^–, SO₄ ^2–, SO₃ ^2–, PO₄ ^3–, organischen Phosphaten, organischen Phosphonaten, organischen Sulfaten, organischen Sulfonaten und aromatischen N-Donoren, wie Pyridinen, Pyrazinen, Pyrazolen, Imidazolen, Benzimidazolen, Pyrimidinen, Triazolen und Thiazolen, wobei R H, wahlweise substituiertes Alkyl, wahlweise substituiertes Aryl ist.

In the broadest sense, the transition metal bleach catalyst of the present invention comprises:

• i) 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), Ni (I), Ni (II), Ni (III), Cu (I), Cu (II), Cu (III), Cr (II), Cr (III ), Cr (IV), Cr (V), Cr (VI), V (III), 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 (III), Fe (IV), Cr (II), Cr (III), Cr (IV), Cr (V), Cr (VI), and mixtures thereof; and
• ii) a cross-bridged macropolycyclic ligand coordinated to the same transition metal by four or five donor atoms, said ligand comprising:
• a) an organic macrocyclic 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 bonds of 2 or 3 non-donor atoms, with two to five (preferably three to four, yet more preferably four) of these donor atoms are coordinated to the same transition metal atom in the complex;
• b) a cross-linked chain covalently linking at least two non-adjacent donor atoms of the organic macrocyclic ring, wherein the covalently bonded, non-adjacent donor atoms are bridgehead donor atoms coordinated to the same transition metal in the complex, and wherein the chain is substituted with the Crossbridges 2 to about 10 atoms (preferably, the cross-bridged chain is selected from 2, 3 or 4 non-donor atoms and 4-6 non-donor atoms with another donor atom);
• c) optionally one or more non-macropolycyclic ligands, preferably selected from the group consisting of H ₂ O, ROH, NR _3, RCN, OH ^-, OOH ^-, RS ^-, RO ^-, RCOO ^-, OCN ^-, SCN ^-, organic, SO ₄ ^2-, SO ₃ ^2-, PO ₄ ^3-, organic phosphates, ^- N ₃ ^-, CN ^-, F ^-, Cl ^-, Br ^-, I ^-, O ₂ ^-, NO ₃ ^-, NO ₂ Phosphonates, organic sulfates, organic sulfonates and aromatic N donors such as pyridines, pyrazines, pyrazoles, imidazoles, benzimidazoles, pyrimidines, triazoles and thiazoles, wherein R is H, optionally substituted alkyl, optionally substituted aryl.

• a) einem makropolycyclischen Liganden der Formel (I) mit Querbrücken mit einer Dentizität von 4 oder 5:
  
• b) einem makropolycyclischen Liganden der Formel (II) mit Querbrücken mit einer Dentizität von 5 oder 6:
  
• c) dem makropolycyclischen Liganden der Formel (III) mit Querbrücken mit einer Dentizität von 6 oder 7:
  
  worin jede E-Einheit die Gruppierung mit folgender Formel darstellt: (CR_n)_a-X-(CR_n)_a' worin X ausgewählt ist aus der Gruppe, bestehend aus Sauerstoff, Schwefel, -NR-, Phosphor, oder X eine kovalente Bindung darstellt, worin E folgende Formel hat: (CR_n)_a-(CR_n)_a' für jede E-Einheit die Summe von a + a' unabhängig von 1 bis 5 ausgewählt ist; jede G-Einheit eine (CR_n)_b-Gruppierung ist; jede R-Einheit unabhängig von den anderen ausgewählt ist aus H, Alkyl, Alkenyl, Alkynyl, Aryl, Alkylaryl und Heteroaryl, oder zwei oder mehr R-Einheiten kovalent verknüpft sind, um einen aromatischen, heteroaromatischen Ring oder einen Cycloalkyl- oder Heterocycloalkylring zu bilden; jede D-Einheit ein Donoratom ist, das unabhängig von den anderen ausgewählt ist aus der Gruppe, bestehend aus Stickstoff, Sauerstoff, Schwefel und Phosphor, und mindestens zwei Atome, die D-Einheiten umfassen, Brückenkopf-Donoratome sind, die an das Übergangsmetall koordiniert sind; B-Einheiten ein Kohlenstoffatom, eine D-Einheit oder ein Cycloalkylring oder ein heterocyclischer Ring sind; jedes n eine ganze Zahl ist, die unabhängig ausgewählt ist aus 1 und 2, was die Valenz der Kohlenstoffatome, an welche die R-Einheiten kovalent gebunden sind, vervollständigt; jedes n' eine ganze Zahl ist, die unabhängig ausgewählt ist aus 0 und 1, was die Valenz des D-Donoratoms, an das die R-Gruppierungen kovalent gebunden sind, vervollständigt; jedes n'' eine ganze Zahl ist, die unabhängig aus 0, 1 und 2 ausgewählt ist, was die Valenz der B-Atome, an welche die R-Gruppierungen kovalent gebunden sind, vervollständigt; jedes a und jedes a' eine ganze Zahl sind, die unabhängig aus 0 bis 5 ausgewählt sind, wobei die Summe aller a + a'-Werte in dem Liganden der Formel (I) im Bereich von etwa 8 bis etwa 12 liegt; die Summe aller a + a'-Werte in dem Liganden der Formel (II) im Bereich von etwa 10 bis etwa 15 liegt und die Summe aller a + a'-Werte in dem Liganden der Formel (III) im Bereich von etwa 12 bis etwa 18 liegt; jedes b eine ganze Zahl ist, die unabhängig aus 0 bis 9 ausgewählt ist, oder in jeder der obigen Formeln eine oder mehrere der (CR_n)_b-Gruppierungen, die jedes beliebige der D-Atome kovalent mit dem B-Atom verbinden, fehlt, solange mindestens zwei (CR_n)_b zwei der D-Donoratome kovalent an das B-Atom in der Formel binden und die Summe aller b-Indizes im Bereich von etwa 2 bis etwa 5 liegt.

The preferred cross-bridged macropolycyclic ligands are selected from the group consisting of:

• a) a macropolycyclic ligand of the formula (I) having cross-links with a denticity of 4 or 5:
  
• b) a macropolycyclic ligand of formula (II) having cross-links with a denticity of 5 or 6:
  
• c) the macropolycyclic ligand of the formula (III) with transverse bridges having a denticity of 6 or 7:
  
  wherein each E unit represents the grouping with the formula: (CR _n ) _a -X- (CR _n ) _{a '} wherein X is selected from the group consisting of oxygen, sulfur, -NR-, phosphorus, or X is a covalent bond, wherein E has the formula: (CR _n ) _a - (CR _n ) _{a '} for each E unit, the sum of a + a 'is selected independently of 1 to 5; each G unit is a (CR _n ) _b grouping; each R moiety independently of the others is selected from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl and heteroaryl, or two or more R moieties are covalently linked to form an aromatic, heteroaromatic ring or a cycloalkyl or heterocycloalkyl ring ; each D unit is a donor atom independently of the others selected from the group consisting of nitrogen, oxygen, sulfur and phosphorus, and at least two atoms comprising D units are bridgehead donor atoms which coordinate to the transition metal are; B units are a carbon atom, a D unit or a cycloalkyl ring or a heterocyclic ring; each n is an integer independently selected from 1 and 2, which completes the valency of the carbon atoms to which the R moieties are covalently bonded; each n 'is an integer independently selected from 0 and 1, which completes the valency of the D donor atom to which the R moieties are covalently bonded; each n '' is an integer independently selected from 0, 1 and 2, which completes the valency of the B atoms to which the R moieties are covalently bonded; each a and each a 'are an integer independently selected from 0 to 5, the sum of all a + a' values in the ligand of formula (I) being in the range of about 8 to about 12; the sum of all a + a 'values in the ligand of formula (II) is in the range of about 10 to about 15 and the sum of all a + a' values in the ligand of formula (III) is in the range of about 12 to is 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 ) _b moieties covalently linking any of the D atoms to the B atom is absent as long as at least two (CR _n ) _b covalently bind two of the D donor atoms to the B atom in the formula and the sum of all b indices ranges from about 2 to about 5.

A Further description of the bleaching catalysts of the invention is in WO 98/39406 A1 on September 11, 1998, WO 98/39098 A1, published September 11, 1998 1998, and WO 98/39335 A1 on September 11, 1998, all of which are incorporated herein by reference are included.

The used in this patent nomenclature to describe the transition metal bleach catalyst is the same nomenclature style used in the above References is used. The chemical names of one or however, more of the ligands described herein may be derived from the according to the rules of the International Union of Pure and Applied Chemistry (IUPAC) assigned name. For example, has one for the For the purposes of the present invention, preferred ligand, 5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane, the IUPAC name 4,11-dimethyl-1,4,8,11-tetraazabicyclo [6.6.2] hexadecane.

Transition-metal bleach catalysts useful in the compositions of the invention may generally comprise known compounds when consistent with the definition of the invention, and more preferably any of a large number of novel compounds expressly contemplated for use herein Washing and cleaning agents are designed. Non-limiting examples of suitable catalysts according to the invention include:
Manganese (II) 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
Diaqua-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) hexafluorophosphate
Aqua-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (III) hexafluorophosphate
Diaqua-4,10-dimethyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane Manganese (II) hexafluorophosphate
Diaqua-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) tetrafluoroborate
Diaqua-4,10-dimethyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane Manganese (II) tetrafluoroborate
Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (III) hexafluorophosphate
Manganese (II) Dichloro-5,12-di-n-butyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane
Manganese (II) Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane
Manganese (II) Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane
Manganese (II) Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane
Manganese (II) Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane
Iron (II) Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane
Iron (II) 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
Copper (II) Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane
Cobalt (II) Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane
Cobalt (II) Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane
Manganese (II) Dichloro-5,12-dimethyl-4-phenyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Manganese (II)
Manganese (II) Dichloro-4,10-dimethyl-3-phenyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane;
Manganese (II)
Manganese (II) Dichloro-5,12-dimethyl-4,9-diphenyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Manganese (II)
Manganese (II) Dichloro-4,10-dimethyl-3,8-diphenyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane;
Manganese (II)
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)
Manganese (II) Dichloro-2,4,5,9,11,12-hexamethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane,
Manganese (II)
Manganese (II) Dichloro-2,3,5,9,10,12-hexamethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Manganese (II)
Manganese (II) Dichloro-2,2,4,5,9,9,11,12-octamethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane
Manganese (II) Dichloro-2,2,4,5,9,11,11,12-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)
Manganese (II) Dichloro-3,5,10,12-tetramethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Manganese (II)
Manganese (II) Dichloro-3-butyl-5,10,12-trimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane;
Manganese (II)
Manganese (II) Dichloro-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane
Manganese (II) Dichloro-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane
Iron (II) Dichloro-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane
Iron (II) Dichloro-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane
Manganese (II) aqua-chloro-2- (2-hydroxyphenyl -) - 5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane
Manganese (II) aqua-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)
Manganese (II) chloro-10- (2-hydroxybenzyl) -4-methyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane
Chloro-5-methyl-L2- (2-picolyl) -1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) chloride
Chloro-4-methyl-10- (2-picolyl) -1,4,7,10-tetraazabicyclo [5.5.2] tetradecane Manganese (II) chloride
Manganese (III) Dichloro-5- (2-sulfato) dodecyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane
Manganese (II) aqua-chloro-5- (2-sulfato) dodecyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane
Manganese (II) aqua-chloro-5- (3-sulfonopropyl) -12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane
Dichloro-5- (trimethylammoniumpropyl) dodecyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (III) chloride
Manganese (II) Dichloro-5,12-dimethyl-1,4,7,10,13-pentaazabicyclo [8.5.2] heptadecane
Manganese (II) Dichloro-14,20-dimethyl-1,10,14,20-tetraazatriyclo [8.6.6] docosa-3 (8), 4,6-triene;
Manganese (II)
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) Dichloro-3,10-up (butylcarboxy) -5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane
Manganese (II) -diaqua-3,10-dicarboxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane
Chloro-20-methyl-1,9,20,24,25-pentaazatetracyclo [7.7.7.1 ^3,7 .1 ^11,15 .] Pentacosa-3,5,7 (24), 11,13,15 (25) -hexaen manganese (II) hexafluorophosphate
Trifluoromethanesulfone-20-methyl-1,9,20,24,25-pentaazatetracyclo [7.7.7.1 ^3,7 .1 ^11,15 .] Pentacosa-3,5,7 (24), 11,13,15 (25) -hexaen manganese (II) trifluoromethanesulfonate
Trifluoromethanesulfone-20-methyl-1,9,20,24,25-pentaazatetracyclo [7.7.7.1 ^3,7 .1 ^11,15 .] Pentacosa-3,5,7 (24), 11,13,15 (25) -hexaen iron (II) trifluoromethanesulfonate
Chloro-5,12,17-trimethyl-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) hexafluorophosphate
Chloro-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) chloride
Manganese (II) dichloro-5,12,15,16-tetramethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane
Manganese (II) chloro-5-methyl-12- (2'-oxybenzyl) -1,5,8,12-tetraazabicyclo [6.6.2] hexadecane.

preferred Complexes used as transition-metal bleach catalysts can be used Include more general not only monometallic, mononuclear species such as those shown hereinabove, but also bimetallic or trimetallic species or cluster species. Monometallic, mononuclear Complexes are preferred. As defined herein, a monometallic transition metal bleach catalyst only one transition metal atom per mole of the complex. A monometallic, mononuclear complex is one in which every donor atom of the essential macrocyclic Ligands to the same transition metal atom is bound, that is, that the essential ligand does not bridge two or more transition metal atoms.

stabilizer

Antioxidant

A Type of preferred stabilizer according to the invention are Antioxidant. The compositions of the present invention comprise an effective amount of the antioxidant, of about 0.01 Wt%, more preferably about 0.1 wt%, most preferably from about 0.2 wt% to 10 wt%, preferably to about 5% by weight, more preferably to about 1% by weight, of antioxidant. Preferably, the antioxidant is a radical scavenger.

worin R lineares oder verzweigtes C₁-C₂₂-Alkyl, vorzugsweise Methyl oder verzweigtes C₃-C₆-Alkyl; C₃-C₆-Alkoxy, vorzugsweise Methoxy ist; R¹ ein verzweigtes C₃-C₆-Alkyl, vorzugsweise tert-Butyl ist; x 1 oder 2 ist.A class of antioxidants suitable for use in the present invention are the alkylated phenols having the general formula:

wherein R is linear or branched C ₁ -C ₂₂ -alkyl, preferably methyl or branched C ₃ -C ₆ -alkyl; C ₃ -C ₆ alkoxy, preferably methoxy; R ^{1 is} a branched C ₃ -C ₆ alkyl, preferably tert-butyl; x is 1 or 2.

worin R¹ und R² jeweils unabhängig voneinander C₁-C₄-Alkyl sind oder R¹ und R² zusammengenommen werden können, um eine cyclische C₅-C₆-Hydrocarbyleinheit zu bilden; R⁴ C₁-C₆-Alkyl ist; R⁵ Wasserstoff oder -C(O)R³ ist, worin R³ Wasserstoff oder C₁-C₁₉-Alkyl ist; R⁶ C₁-C₆-Alkyl ist; R⁷ Wasserstoff oder C₁-C₆-Alkyl ist; X -CH₂OH oder -CH₂A ist, worin A eine Stickstoff umfassende Einheit, Phenyl oder substituiertes Phenyl ist. Bevorzugte Stickstoff umfassende A-Einheiten umfassen Amino, Pyrrolidino, Piperidino, Morpholino, Piperazino und Mischungen davon.Another class of antioxidants suitable for use in the present invention are benzofuran derivatives having the formula:

wherein R ¹ and R ^{2 are} each independently C ₁ -C ₄ alkyl, or R ¹ and R ² can be taken together to form a cyclic C ₅ -C ₆ hydrocarbyl moiety; R ^{4 is} C ₁ -C ₆ alkyl; R ^{5 is} hydrogen or -C (O) R ³ , wherein R ^{3 is} hydrogen or C ₁ -C ₁₉ alkyl; R ^{6 is} C ₁ -C ₆ alkyl; R ^{7 is} hydrogen or C ₁ -C ₆ alkyl; X is -CH ₂ OH or -CH ₂ A, where A is a nitrogen comprising moiety, phenyl or substituted phenyl. Preferred nitrogen containing A moieties include amino, pyrrolidino, piperidino, morpholino, piperazino and mixtures thereof.

Not restrictive Examples more suitable for use in the present invention Antioxidants include phenols, inter alia 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, mixture of 2- and 3-tert-butyl-4-methoxyphenol, and other ingredients, including propyl gallate, tert-butyl hydroquinone, benzoic acid derivatives, such as methoxybenzoic acid, methylbenzoic dichlorobenzoic, dimethylbenzoic, 5-hydroxy-2,2,4,6,7-pentamethyl-2,3-dihydro-1-benzofuran-3-one, 5-hydroxy-3-methylene-2,2,4,6,7-pentamethyl 2,3-dihydrobenzofuran, 5-Benzyloxy-3-hydroxymethyl-2,2,4,6,7-pentamethyl-2,3-dihydro-1-benzofuran, 3-hydroxymethyl-5-methoxy-2,2,4,6,7-pentamethyl-2,3-dihydro-1-benzofuran.

reducing agent

A Type of preferred stabilizer according to the invention are Reducing agent. The compositions of the present invention comprise an effective amount of one or more reducing agents, from 0.001 wt%, more preferably from about 0.01 wt%, most preferably about 0.02 wt.% To 1 wt.%, Preferably to about 0.5 wt.%, More preferably until about 0.1% by weight of reducing agent. Preferably, the reducing agent is an inorganic compound.

Not restrictive examples for Reducing agents include compounds capable of sulfite ion such as sodium sulfite, potassium sulfite, ammonium sulfite, Sodium bisulfite, sodium bisulfite, potassium bisulfite, potassium bisulfite, Pyrosulfite salts, sodium borohydride, lithium borohydride, lithium aluminum isopropoxide and mixtures thereof.

application method

The The present invention further relates to an application method stabilized bleach catalysts without the need a source of peroxide to remove dirt and stains from fabric.

• A) eine katalytisch wirksame Menge eines Übergangsmetall-Bleichmittelkatalysators, der ein Komplex eines Übergangsmetalls und eines querverbrückten makropolycyclischen Liganden ist;
• B) eine wirksame Menge eines Stabilisierungsmittels, wobei das Mittel ausgewählt ist aus i) 0,01 bis 10 Gew.-% an einem oder mehreren Antioxidationsmitteln; ii) 0,001 bis 1 Gew.-% an einem oder mehreren Reduktionsmitteln; iii) und Mischungen davon; und
• C) zu übrigen Teilen Träger und andere Zusatzbestandteile;

mit der Maßgabe, dass die Konzentration des Übergangsmetall-Bleichmittelkatalysators in der Lösung mindestens ungefähr 0,01 ppb ist und die Zusammensetzung im Wesentlichen frei von jeglichen organischen oder anorganischen Persauerstoffverbindungen ist.The present invention therefore relates to a method of bleaching stains and stains on fabric in the absence of a bleach, the method comprising the step of contacting the fabric to be cleaned with an aqueous or nonaqueous solution containing a composition substantially free from a peroxide source and 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;
• B) an effective amount of a stabilizing agent, wherein the agent is selected from i) 0.01 to 10% by weight of one or more antioxidants; ii) from 0.001 to 1% by weight of one or more reducing agents; iii) and mixtures thereof; and
• C) other parts Carrier and other additional components;

with the proviso that the concentration of the transition metal bleach catalyst in the solution is at least about 0.01 ppb and the composition is substantially free of any organic or inorganic peroxygen compounds.

Preferably, the solution comprising the transition metal bleach catalyst has a catalyst solution concentration of about 1 ppb, more preferably about 10 ppb, even more preferably about 100 ppb. For example, 100 ppb (parts per billion) is a solution containing 0.00001 wt% kata includes lysator. As defined above, solutions containing less than 0.001% of a peroxide source are solutions that are "substantially free" of any organic or inorganic peroxygen compounds.

Method, the whole on large-scale Aimed at bleaching, for example an industrial or manufacturing process, can a higher one Catalyst concentration, for example 1 ppm or higher, use to the contact time of the substance with the catalyst-containing solution reduce.

additional ingredients

The Bleaching, pre-soaking, pretreatment, laundry or machine dishwashing or Hard surface cleaning compositions of the present invention, whether granular, solid (piece), gel or liquid, can Furthermore one or more carriers and additional components.

• a) eine katalytisch wirksame Menge eines Übergangsmetall-Bleichmittelkatalysators, der ein Komplex eines Übergangsmetalls und eines querverbrückten makropolycyclischen Liganden ist; und
• b) wahlweise von ungefähr 0,001 Gew.-% bis ungefähr 90 Gew.-% ein oder mehrere Farbstofffixierungsmittel;
• c) wahlweise von ungefähr 0,01 Gew.-% bis ungefähr 50 Gew.-% ein oder mehrere Cellulose-reaktive Farbstofffixierungsmittel;
• d) wahlweise von ungefähr 0,01 Gew.-% bis ungefähr 15 Gew.-% einen Chlor-Radikalfänger;
• e) wahlweise von ungefähr 0,005 Gew.-% bis ungefähr 1 Gew.-% einen oder mehrere Kristallisationsverzögerer;
• f) wahlweise von ungefähr 0,01 Gew.-% bis ungefähr 20 Gew.-% ein Gewebeabrieb reduzierendes Polymer;
• g) wahlweise von ungefähr 1 Gew.-% bis ungefähr 12 Gew.-% einen oder mehrere flüssige Träger;
• h) wahlweise von ungefähr 0,001 Gew.-% bis ungefähr 1 Gew.-% ein Enzym;
• i) wahlweise von ungefähr 0,01 Gew.-% bis ungefähr 8 Gew.-% eine Polyolefinemulsion oder -suspension;
• j) wahlweise von ungefähr 0,01 Gew.-% bis ungefähr 0.2 Gew.-% ein Stabilisierungsmittel;
• k) wahlweise von ungefähr 1 Gew.-% bis ungefähr 80 Gew.-% einen Gewebeweichmacher;
• l) wahlweise weniger als ungefähr 15 Gew.-% ein Hauptlösungsmittel; und
• m) wahlweise von ungefähr 0,01 Gew.-%, vorzugsweise von 0,1 Gew.-% bis 60 Gew.-%, vorzugsweise bis 30 Gew.-% ein oder mehrere Tenside, wobei die Tenside ausgewählt sind aus der Gruppe, bestehend aus anionischen, kationischen, nichtionischen, ampholytischen, zwitterionischen Tensiden und Mischungen davon.

Compositions according to the 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 fixatives;
• 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 radical scavenger;
• e) optionally from about 0.005% to about 1% by weight of one or more crystallization retarders;
• f) optionally from about 0.01% to about 20% by weight of a tissue 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 polyolefin 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 conditioner;
• l) optionally less than about 15% by weight of a principal solvent; and
• m) optionally from about 0.01% by weight, preferably from 0.1% to 60% by weight, preferably to 30% by weight of one or more surfactants, the surfactants being selected from the group consisting of consisting of anionic, cationic, nonionic, ampholytic, zwitterionic surfactants and mixtures thereof.

surfactants

The Bleaching, soaking, pretreatment and laundry detergent compositions of the present invention at least about 0.01 wt%, preferably from about 0.1 wt% to about 60 wt%, preferably to about 30% by weight of a detergent surfactant system depending on the embodiment from one or more types of surfactants that are surfactant categories selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants and mixtures thereof. Within each surfactant category, more than one type of surfactant may be used selected become. For example, it is preferably in the solid (i.e., granular) and viscous semi-solid (i.e., gel, pasty, etc.) systems of the present invention Invention surfactant preferably in a concentration of about 0.1% by weight to 60% by weight, preferably to about 30% by weight of the composition available.

• a) C₁₁-C₁₈-Alkylbenzolsulfonate (LAS);
• b) primäre, verzweigtkettige und statistische C₁₀-C₂₀-Alkylsulfate (AS);
• c) sekundäre (2,3) C₁₀-C₁₈-Alkylsulfate mit der Formel:
  
  worin x und (y + 1) ganze Zahlen von mindestens ungefähr 7, vorzugsweise mindestens ungefähr 9 sind; die Tenside sind in US-Patent Nr. 3,234,258, Morris, erteilt am 8. Februar 1966, US-Patent Nr. 5,075,041, Lutz, erteilt am 24. Dezember 1991, US-Patent Nr. 5,349,101, Lutz et al., erteilt am 20. September 1994, und US-Patent Nr. 5,389,277, Prieto, erteilt am 14. Februar 1995, offenbart, die jeweils durch Bezugnahme hierin eingeschlossen sind;
• d) C₁₀-C₁₈-Alkylalkoxysulfate (AE_xS), worin vorzugsweise x von 1–7 ist;
• e) C₁₀-C₁₈-Alkylalkoxycarboxylate, die vorzugsweise 1–5 Ethoxyeinheiten umfassen;
• f) C₁₂-C₁₈-Alkylethoxylate, C₆-C₁₂-Alkylphenolalkoxylate, worin die Alkoxylateinheiten eine Mischung aus Ethylenoxy- und Propylenoxyeinheiten sind, C₁₂-C₁₈-Alkohol- und C₆-C₁₂-Alkylphenolkondensate mit Ethylenoxid/Propylenoxid-Blockpolymeren, unter anderem Pluronic^® von BASF, die in US-Patent Nr. 3,929,678, Laughlin et al., erteilt am 30. Dezember 1975, offenbart sind, durch Bezugnahme hierin eingeschlossen;
• g) Alkylpolysaccharide, wie in US-Patent Nr. 4,565,647 Llenado, erteilt am 26. Januar 1986, offenbart, durch Bezugnahme hierin eingeschlossen;
• h) Polyhydroxyfettsäureamide mit der Formel:
  
  worin R⁷ C₅-C₃₁-Alkyl ist; R⁸ ausgewählt ist aus der Gruppe, bestehend aus Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Hydroxyalkyl, Q eine Polyhydroxyalkyleinheit mit einer linearen Alkylkette mit mindestens 3 Hydroxylen, die direkt an die Kette gebunden sind, oder ein alkoxyliertes Derivat davon ist; bevorzugtes Alkoxy ist Ethoxy oder Propoxy und Mischungen davon; bevorzugtes Q ist von einem reduzierenden Zucker in einer reduktiven Aminierung abgeleitet, mehr bevorzugt ist Q eine Glycityleinheit; Q ist mehr bevorzugt ausgewählt aus der Gruppe, bestehend aus -CH₂(CHOH)_nCH₂OH, -CH(CH₂OH)(CHOH)_n–1CH₂OH, -CH₂(CHOH)₂-(CHOR')(CHOH)CH₂OH und alkoxylierten Derivaten davon, worin n eine ganze Zahl von 3 bis einschließlich 5 ist, und R' Wasserstoff oder ein cyclisches oder aliphatisches Monosaccharid ist, die in US-Patent Nr. 5,489,393, Connor et al., erteilt am 6. Februar 1996 und US-Patent Nr. 5,45,982, Murch et al., erteilt am 3. Oktober 1995, beschrieben sind, beide durch Bezugnahme hierin eingeschlossen.

Nonlimiting examples of suitable surfactants herein include:

• a) C ₁₁ -C ₁₈ alkyl benzene sulphonates (LAS);
• b) primary, branched and random C ₁₀ -C ₂₀ alkyl sulfates (AS);
• c) secondary (2,3) C ₁₀ -C ₁₈ alkyl sulfates having the formula:
  
  wherein x and (y + 1) are integers of at least about 7, preferably at least about 9; the surfactants are described in U.S. Patent No. 3,234,258, Morris, issued February 8, 1966, U.S. Patent No. 5,075,041, Lutz, issued December 24, 1991, U.S. Patent No. 5,349,101, Lutz et al., Issued September 20, 1994, and U.S. Patent No. 5,389,277, Prieto, issued February 14, 1995, each of which is incorporated herein by reference References are included herein;
• d) C ₁₀ -C ₁₈ alkyl alkoxy sulfates (AE _x S), wherein preferably x is 1-7;
• e) C ₁₀ -C ₁₈ -alkyl alkoxycarboxylates, which preferably comprise 1-5 ethoxy units;
• f) C ₁₂ -C ₁₈ alkyl ethoxylates, C ₆ -C ₁₂ alkyl phenol alkoxylates wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units, C ₁₂ -C ₁₈ alcohol and C ₆ -C ₁₂ alkylphenol condensates with ethylene oxide / propylene oxide ., block polymers, inter alia Pluronic ^® ex BASF which et in U.S. Patent No. 3,929,678, Laughlin al, issued December 30, 1975, are disclosed, incorporated herein by reference;
• g) alkyl polysaccharides as disclosed in U.S. Patent No. 4,565,647 Llenado, issued January 26, 1986, incorporated herein by reference;
• h) polyhydroxy fatty acid amides having the formula:
  
  wherein R ^{7 is} C ₅ -C ₃₁ alkyl; R ^{8 is} selected from the group consisting of hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, Q is a polyhydroxyalkyl moiety having a linear alkyl chain with at least 3 hydroxyls directly attached to the chain alkoxylated derivative thereof; preferred alkoxy is ethoxy or propoxy and mixtures thereof; preferred Q is derived from a reducing sugar in a reductive amination, more preferably Q is a glycyl moiety; Q is more preferably selected from the group consisting of -CH ₂ (CHOH) _n CH ₂ OH, -CH (CH ₂ OH) (CHOH) _n-1 CH ₂ OH, -CH ₂ (CHOH) ₂ - (CHOR ' ) (CHOH) CH ₂ OH and alkoxylated derivatives thereof, wherein n is an integer from 3 to 5, inclusive, and R 'is hydrogen or a cyclic or aliphatic monosaccharide described in U.S. Patent No. 5,489,393, Connor et al., issued February 6, 1996 and U.S. Patent No. 5,455,982, Murch et al., issued October 3, 1995, both incorporated herein by reference.

mittelkettig verzweigten Alkylsulfaten mit der Formel:

und mittelkettig verzweigten Alkylalkoxysulfaten mit der Formel:

worin die Gesamtanzahl an Kohlenstoffatomen in der verzweigten primären Alkyleinheit dieser Formeln (einschließlich der R-, R¹- und R²-Verzweigung, jedoch nicht einschließlich der Kohlenstoffatome, die eine EO/PO-Alkoxyeinheit umfassen) von 14 bis 20 ist und worin des Weiteren für diese Tensidmischung die durchschnittliche Gesamtanzahl an Kohlenstoffatomen in den verzweigten primären Alkyleinheiten mit der vorstehenden Formel im Bereich von mehr als 14,5 bis ungefähr 17,5 ist (vorzugsweise von ungefähr 15 bis ungefähr 17); R, R¹, und R² jeweils unabhängig ausgewählt sind aus Wasserstoff, C₁-C₃-Alkyl und Mischungen davon, vorzugsweise Methyl; mit der Maßgabe, dass R, R¹ und R² nicht alle Wasserstoff sind und, wenn z 1 ist, mindestens R oder R¹ nicht Wasserstoff ist. M ist ein wasserlösliches Kation und kann mehr als eine Kationenart umfassen, zum Beispiel eine Mischung aus Natrium und Kalium. Der Index w ist eine ganze Zahl von 0 bis 13; x ist eine ganze Zahl von 0 bis 13; y ist eine ganze Zahl von 0 bis 13; z ist eine ganze Zahl von mindestens 1; mit der Maßgabe, dass w + x + y + z von 8 bis 14 ist. EO und PO stehen für Ethylenoxyeinheiten bzw. Propylenoxyeinheiten mit der Formel:

jedoch sind auch andere Alkoxyeinheiten, unter anderem 1,3-Propylenoxy, Butoxy und Mischungen davon als Alkoxyeinheiten, die an die mittelkettig verzweigten Alkyleinheiten gebunden sind, geeignet.The bleaching, soaking, pretreatment and laundry detergent compositions of the present invention may also comprise from about 0.001% to about 100% of one or more (preferably a mixture of two or more) mid-chain branched surfactants, preferably mid-chain branched alkylalkoxy alcohols having the formula :

medium chain branched alkyl sulfates having the formula:

and mid-chain branched alkyl alkoxy sulfates having the formula:

wherein the total number of carbon atoms in the branched primary alkyl moiety of these formulas (including the R, R ¹ and R ² branch but not including the carbon atoms comprising an 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 primary alkyl moieties of the above formula ranges from greater than 14.5 to about 17.5 (preferably from about 15 to about 17); R, R ¹ and R ^{2 are} each independently selected from hydrogen, C ₁ -C ₃ alkyl and mixtures thereof, preferably methyl; with the proviso that R, R ¹ and R ^{2 are} not all hydrogen and, when z is 1, at least R or R ^{1 is} not hydrogen. M is a water-soluble cation and may include more than one type of cation, for example, a mixture of sodium and potassium. The index w 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; with the proviso that w + x + y + z is from 8 to 14. EO and PO stand for ethyleneoxy units or propyleneoxy units having the formula:

however, other alkoxy units, including but not limited to 1,3-propyleneoxy, butoxy and mixtures thereof, are also useful as alkoxy units attached to the mid-chain branched alkyl moieties.

The Medium chain branched surfactants are preferably mixtures that a surfactant system. Therefore, the index gives m when the surfactant system an alkoxylated surfactant comprises the average degree of alkoxylation within the surfactant mixture. As such, the index is at least m approximately 0.01, preferably within the range of about 0.1, more preferably about 0.5, most preferably from about 1 to about 30, preferably until about 10, more preferably to about 5. When considering a middle-chain branched surfactant system, which comprises only alkoxylated surfactants, the index m represents a distribution the average degree of alkoxylation corresponding to m, or a single special chain with alkoxylation (e.g. B. ethoxylation and / or propoxylation) of exactly the number Units corresponding to m.

oder die Formel

worin a, b, d und e solche Ganzzahlen sind, dass a + b von 10 bis 16 ist und d + e von 8 bis 14 ist; M aus Natrium, Kalium, Magnesium, Ammonium und substituiertem Ammonium und Mischungen davon ausgewählt ist.The preferred mid-chain branched surfactants of the present invention suitable for use in the surfactant systems of the present invention have the formula:

or the formula

wherein a, b, d and e are such integers 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 branched medium chain Surfactants include, are preferably in two embodiments formulated. A first preferred embodiment comprises medium-chain branched surfactants consisting of a feed that is 25% or less mid-chain branched alkyl moieties, are formed. Therefore, the mid-chain branched surfactant component is included blending with other conventional ones Surfactants 25% or less surfactant molecules that are non-linear surfactants.

A second preferred embodiment comprises medium-chain branched surfactants consisting of a feedstock, from about 25% to about 70% of medium chain branched alkyl units. Therefore, the mid-chain branched surfactant component is included blending with other conventional ones Surfactants about 25% to about 70% surfactant molecules, which are nonlinear surfactants.

worin L eine acyclische Hydrocarbyleinheit, die 6 bis 18 Kohlenstoffatome umfasst, ist; R¹, R² und R³ jeweils unabhängig Wasserstoff oder C₁-C₃-Alkyl sind, mit der Maßgabe, dass R¹ und R² nicht an den Terminus der L-Einheit gebunden sind; M ein wasserlösliches Kation mit der Ladung q ist, worin a und b zusammengenommen werden, um die Ladungsneutralität zu befriedigen.The surfactant system of the laundry detergent compositions of the present invention may also be from about 0.001% by weight, preferably from about 1% by weight, more preferably from about 5% by weight, most preferably from about 10% to about 100% by weight %, preferably to about 60%, more preferably to about 30% by weight of the surfactant system comprises one or more (preferably a mixture of two or more) mid-chain branched alkylarylsulfonate surfactants, preferably surfactants wherein the aryl moiety comprises a benzene ring the following formula is:

wherein L is an acyclic hydrocarbyl moiety comprising 6 to 18 carbon atoms; R ¹ , R ² and R ^{3 are} each independently hydrogen or C ₁ -C ₃ alkyl, with the proviso that R ¹ and R ^{2 are} not attached to the terminus of L unit are bound; M is a water-soluble cation with the charge q, where a and b are taken together to satisfy the charge neutrality.

Builder

The Compositions of the present invention, especially when they Surfactants include, preferably, one or more detergency builders or builder systems. If present, the compositions include usually at least about 1 wt% builder, preferably about 5 wt%, more preferably of about 10% by weight to about 80% by weight, preferably up to about 50% by weight, more preferably until about 30% by weight of detergent builder.

Of the Share of builder can depend on the purpose of the composition and its desired physical form very fluctuate. If available, include Compositions typically at least about 1% builder. Formulations typically comprise from about 5% to about 50% Wt%, more typically about 5 wt% to about 30 wt% detergent builder. Grainy formulations typically comprise from about 10% to about 80% by weight, more typically about From 15% to about 50% by weight of detergent builder. Lower or higher shares on builder but should not be excluded.

inorganic or P-containing detergent builders shut down the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by tripolyphosphates, pyrophosphates and glassy polymeric metaphosphates), phosphonates, phytic acid, silicates, Carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates, but are not limited to this. In some regions, however, there are builders, which are not phosphates required. It is important that the compositions even in the presence of so-called "weak" builders (compared to phosphate), like citrate, or in the so-called "inadequately adjusted" situation at Zeolite or layered silicate builders can be surprising are very effective.

Examples for silicate builders are the alkali metal silicates described in U.S. Patent No. 4,664,839, Rieck, issued May 12, 1987. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (herein generally abbreviated as "SKS-6").

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

Aluminosilicate builders are useful in the present invention. Examples of suitable aluminosilicate builders are described in U.S. Patent No. 4,274,975, Corkhill et al., Incorporated herein by reference. Aluminosilicate builders are of great importance in most currently available granular heavy duty detergent compositions and may also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the following empirical formula: M _z (zAlO _{2) y]} .xH ₂ O wherein z and y are integers of at least 6, the mole ratio of z to y is in the range of 1.0 to about 0.5, and x is an integer of about 15 to about 264. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations zeolite A, zeolite P (B), zeolite MAP and zeolite X.

organic Detergent builders, the for which are suitable for the purposes of the present invention include one size Variety of polycarboxylate compounds, but are not on these are limited. As used herein, "polycarboxylate" refers to compounds with several carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builder may generally be used in the composition Acid form added but may also be added in the form of a neutralized salt become. When used in salt form, alkali metals, such as Sodium, potassium and lithium, or alkanolammonium salts are preferred.

Suitable ones are disclosed in U.S. Patent No. 3,128,287, Berg, issued April 7, 1964, U.S. Patent No. 3,635,830, Lamberti et al., Issued January 18, 1972, U.S. Patent No. 4,663,071, Bush et al., issued May 5, 1987, U.S. Patent No. 3,923,679, Rapko, issued December 2, 1975; U.S. Patent No. 4,158,635, Crutchfield et al., issued to On June 19, 1979, U.S. Patent No. 4,120,874, Crutchfield et al., Issued October 17, 1978, U.S. Patent No. 4,566,984, Bush, issued January 28, 1986, U.S. Patent No. 4,144,226, Crutchfield et al , issued Mar. 13, 1979, and U.S. Patent No. 3,308,067, Diehl, issued Mar. 7, 1967, Diehl, U.S. Patent No. 3,723,322, and U.S. Patent No. 4,102,903, Crutchfield et al on July 25, 1978, and further discloses U.S. Patent Nos. 3,159,581, 3,213,030, 3,422,021, 3,400,148, and 3,422,137.

Citrate builders, for example, citric acid and soluble Salts thereof (especially the sodium salt) are due to their Availability from renewable resources and their biodegradability especially important polycarboxylate builders for liquid full-washing detergent formulations. Citrate can also in grainy Compositions, especially in combination with zeolite and / or Layered silicate builders, to be used. Oxydisuccinates are in such Compositions and combinations are also particularly useful.

dispersants

A Description of other suitable polyalkyleneimine dispersants, optionally with the bleach-stable dispersants of present invention can be found in US Patent No. 4,597,898, Vander Meer, issued July 1, 1986, European Patent Application 111,965, Oh and Gosselink, published on June 27, 1984, the European Patent Application 111,984, Gosselink, published June 27, 1984, the European Patent Application 112,592, Gosselink, published July 4, 1984, U.S. Pat. No. 4,548,744, Connor, issued October 22, 1985 and U.S. Pat U.S. Patent No. 5,565,145, Watson et al., Issued October 15, 1996, all of which are incorporated herein by reference are. However, it can be any suitable clay / soil dispersant or anti-redeposition agents in the laundry compositions of the present invention.

Besides, they are polymeric dispersants, the polymeric polycarboxylates and polyethylene glycols lock in, suitable for use in the present invention. Polymeric polycarboxylate materials can through Polymerization or copolymerization of suitable unsaturated Monomers, preferably in their acid form, are produced. unsaturated monomeric acids, which can be polymerized, To form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or Maleic anhydride), fumaric acid, itaconic, aconitic, mesaconic, citraconic and methylenemalonic acid one. The presence of monomeric portions in the polymeric polycarboxylates, which are not carboxylate radicals, such as vinyl methyl ether, styrene, ethylene etc. is appropriate, provided that such sections do not constitute more than about 40% by weight.

Especially suitable polymeric polycarboxylates can be derived from acrylic acid become. Such acrylic acid-based polymers useful herein are the water-soluble Salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form is preferably in the range of about 2,000 to 10,000, especially 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 for example, include the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. The use of polyacrylates of this type in detergent compositions is for example at Diehl, U.S. Patent No. 3,308,067, issued March 7, 1967.

Acrylic / maleic acid based copolymers may also be used as a preferred ingredient of the dispersing / antiredeposition 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 is preferably in the range of about 2,000, preferably about 5,000, more preferably 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 is generally in the range of 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 may include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate / maleate copolymers of this type are known materials disclosed in European Patent Application No. 66915, published December 15, 1982, and in US Pat EP 193,360 , published September 3, 1986, which also describes such polymers comprising hydroxypropyl acrylate. Other useful dispersants include the maleic acid / acrylic acid / vinyl alcohol terpolymers. Such materials are also in EP 193,360 including, for example, the 45/45/10 terpolymer acrylic acid / maleic acid / vinyl alcohol.

Another polymeric substance that can be included is polyethylene glycol (PEG). PEG can show the performance of a dispersant and act as a clay soil removal / anti redeposition agent. Typical molecular weight ranges for these purposes 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 dispersants can also be used especially in connection with zeolite builders. dispersants, such as polyaspartate, preferably have a molecular weight (average) from about 10,000 on.

soil

The Compositions of the invention can optionally comprise one or more soil release agents. If dirt repellent They generally comprise about 0.01 % By weight, preferably approximately 0.1 wt%, more preferably from about 0.2 wt% to about 10 wt%, preferably to about 5% by weight, more preferably up to about 3% by weight of the composition. Polymeric soil release agents are characterized in that they have both hydrophilic segments to the surface of to hydrophilize hydrophobic fibers, such as polyester and nylon, as well as hydrophobic segments based on hydrophobic fibers store and stick there until the end of the wash cycle and thus as an anchor for serve the hydrophilic segments. This will allow that stains following the treatment with the soil repellent occur in later Washing processes can be removed more easily.

The Following, all of which are incorporated herein by reference, describe soil-repellent polymers that are suitable for use in the present Invention are suitable. U.S. Patent No. 5,728,671, Rohrbaugh et al., granted on 17 March 1998; U.S. Patent No. 5,691,298, Gosselink et al., Issued Nov. 25 1997; U.S. Patent No. 5,599,782, Pan et al., Issued Feb. 4 1997; U.S. Patent No. 5,415,807, Gosselink et al. May 1995; U.S. Patent No. 5,182,043, Morrall et al. January 1993; U.S. Patent No. 4,956,447, Gosselink et al on September 11, 1990; U.S. Patent No. 4,976,879, Maldonado et al. issued on December 11, 1990; U.S. Patent No. 4,968,451, Scheibel et al., issued November 6, 1990; U.S. Patent No. 4,925,577, Borcher, Sr. et al., Issued May 15, 1990; U.S. Patent No. 4,861,512, Gosselink, granted on August 29, 1989; U.S. Patent No. 4,877,896, Maldonado et al., issued October 31, 1989; U.S. Patent No. 4,771,730 to Gosselink et al., issued October 27, 1987; U.S. Patent No. 711,730, Gosselink et al., issued December 8, 1987; U.S. Patent No. 4,721,580, Gosselink, granted on January 26, 1988; U.S. Patent No. 4,000,093, Nicol et al., granted on December 28, 1976; U.S. Patent No. 3,959,230, Hayes on May 25, 1976; US Pat. No. 3,893,929, Basadur, issued on the 8th. July 1975 and European Patent Application 0 219 048 published on April 22, 1987 by Kud et al.

Other suitable soil release agents are described in US Pat. No. 4,201,824, Voilland et al .; US 4,240,918 Lagasse et al .; US 4,525,524 Tung et al .; U.S. Patent No. 4,579,681 Ruppert et al .; U.S. Patent No. 4,220,918; U.S. Patent No. 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 NV, 1974; all incorporated herein by reference.

enzymes

The Detergent and cleaning compositions herein can optionally also contain one or more types of purification enzymes. Such Enzymes can other proteases, amylases, cellulases and lipases. Such Materials are known in the art and are commercially available at such trademarks. You can in the form of suspensions, "marumes" or "prills" in the non-aqueous liquid Detergent compositions can be incorporated herein. Another suitable type of enzyme includes those in the form of slurries of enzymes in nonionic surfactants, e.g. For example, of enzymes derived from Novo Nordisk be marketed under the trade name "SL", or the microencapsulated Enzymes marketed by Novo Nordisk under the trade name "LDP". Suitable enzymes and use concentrations are described in US 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 particularly preferred for use herein. Such prills generally range in size from about 100 to 1,000 microns, more preferably from about 200 to 800 microns, and are suspended throughout the nonaqueous liquid phase of the composition. It has been found that prills in the compositions of the present invention show particularly desirable enzyme stability over time as compared to other enzyme forms. Thus, compositions that use enzyme prills need not have conventional enzyme stabilization contain as they are often used when enzymes are incorporated into aqueous liquid detergents.

however can the enzymes added to the compositions herein, the Form of granules, preferably T-granules have.

"Detersive Enzymes ", as here used means any enzyme with a purifying stain removing or otherwise beneficial effect in one Detergent composition for the laundry, Cleaning hard surfaces or body care. Preferred cleansing enzymes are hydrolases such as proteases, amylases and lipases. Preferred enzymes for Laundry purposes shut down Proteases, cellulases, lipases and peroxidases, but are not limited to these. For automatic dishwashing highly preferred are amylases and / or proteases, including both currently available commercially Species as well as improved species, although through gradual Improvements more and more bleach compatible, a residual level of bleach deactivating susceptibility exhibit.

Examples suitable enzymes include, but are not limited to, Hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, Phospholipases, esterases, cutinases, pectinases, keratanases, reductases, Oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, Tannases, pentosanases, malanases, β-glucanases, arabinosidase, Hyaluronidase, chondroitinases, laccase and known amylases or Mixtures thereof.

Examples such suitable enzymes are disclosed in U.S. Patent Nos. 5,705,464, 5,710,115, 5,576,282, 5,728,671 and 5,707,950.

The cellulases useful in the present invention include cellulases from bacteria or fungi. Preferably, they have a pH optimum between 5 and 12 and a specific activity above 50 CEVU / mg (cellulose viscosity unit). Suitable cellulases are disclosed in U.S. Patent No. 4,435,307, J61078384 and WO96 / 02653, where cellulases are disclosed from fungi made from Humicola insolens, Trichoderma, Thielavia and Sporotrichum, respectively. EP 739 982 describes cellulases isolated from a 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 WO95 / 26398.

Examples Such cellulases are cellulases derived from a strain of Humicola insolens (Humicola grisea var. thermoidea), especially the Humicola strain DSM 1800 become.

Other suitable cellulases are Humicola insolens cellulases having a molecular weight of about 50 KDa, an isoelectric point of 5.5, and 415 amino acids; and a ^~ 43kD endoglucanase from Humicola insolens, DSM 1800, with cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in WO 91/17243. Also suitable cellulases are the EGIII cellulases of Trichoderma longibrachiatum described in WO94 / 21801 to Genencor. Particularly suitable cellulases are the cellulases with color protection properties. Examples of such cellulases are cellulases described in the European patent application EP 91202879.2 , filed November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A / S) are particularly useful. See also WO91 / 17244 and WO91 / 21801. Other suitable cellulases for fabric care and / or having cleaning properties are described in WO96 / 34092, WO96 / 17994 and WO95 / 24471.

cellulases, if present, are usually in the cleaning compositions in concentrations of 0.0001 to 2 wt .-% of pure enzyme, based on the cleaning composition.

Other preferred enzymes that may be included in the cleaning compositions of the present invention include lipases. Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. Suitable lipases include those which show a positive immunological cross-reaction with the antibody against the lipase produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase 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 lipases include Amano-CES, lipases from Chromobacter viscosum, e.g. Chromobacter viscosum var. Lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan, Chromobacter viscosum lipases from US Biochemical Corp., USA, and Disoynth Co., The Netherlands, and lipases from Pseudomo nas gladioli. Especially suitable lipases are lipases such as M1 Lipase ^® and Lipomax® ^® (Gist-Brocades) and Lipolase ^® and Lipolase Ultra ^® (Novo) which have proven to be very effective when used in combination with the inventive compositions. Also suitable are the lipolytic enzymes which are in EP 258,068 , WO 92/05249 and WO 95/22615 to Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 to Unilever.

Also suitable are cutinases [EC 3.1.1.50], which as a special type lipase can be considered, namely as Lipases that do not interfacial activation require. The addition of cutinases to cleaning compositions was z. In WO-A-88/09367 (Genencor), WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever).

lipases and / or cutinases, if any, are in the cleaning compositions usually in concentrations of 0.0001 to 2 wt .-% pure Enzyme, based on the cleaning composition.

In addition to the lipases referred to above, phospholipases may be included in the cleaning compositions of the present invention. Non-limiting examples of suitable phospholipases included: EC 3.1.1.32 phospholipase A1; EC 3.1.1.4 phospholipase A2; EC 3.1.1.5 Lysopholipase; EC 3.1.4.3 Phospholipase C; EC 3.1.4.4. Phospholipase D. Commercially available phospholipases include LECITASE ^® from Novo Nordisk A / S, Denmark and Phospholipase A2 from Sigma. When phospholipases are included in the compositions of the present invention, it is preferred that amylases are also included. Without wishing to be bound by theory, it is believed that the combined action of phospholipase and amylase provides crucial stain removal, particularly on greasy / oily, starchy and highly colored stains and soils. Preferably, the phospholipase and amylase, if present, are included in the compositions of the present invention at a net wet weight ratio of between 4500: 1 and 1: 5, more preferably between 50: 1 and 1: 1.

Suitable examples of proteases are the subtilisins obtained from certain strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN '). One suitable protease with maximum activity throughout the pH range of 8 to 12 is obtained from a strain of Bacillus, by Novo Industries A / S, Denmark, developed and known as ESPERASE ^®, hereinafter "Novo". The preparation of this enzyme and analogous enzymes are described in Novo, GB 1,243,784 Proteolytic enzymes also include modified bacterial serine proteases, such as those described in European Patent Application Serial No. 87 303761.8 (in particular, pages 17, 24 and 98), filed April 28, 1987 hereinafter referred to as "Protease B" and as described in European Patent Application 199,404, Venegas, published October 29, 1986, which relates to a modified bacterial proteolytic serine enzyme, referred to herein as "Protease A." The protease referred to herein is "protease." C ", which is a variant of an alkaline serine protease from Bacillus in which lysine replaces an arginine at position 27 zte, replaced tyrosine valine at position 104, replaced serine asparagine at position 123, and replaced alanine threonine at position 274. Protease C is in EP 90915958.4 , corresponding to WO 91/06637, published May 16, 1991. Genetically modified variants, in particular protease C, are also included herein.

A preferred protease, called "protease D "is designated is a carbonyl hydrolase as described in U.S. Patent No. 5,677,272 and WO95 / 10591 described. Also suitable is a carbonylhydrolase variant the protease with an amino acid sequence described in WO95 / 10591, derived by replacing several amino acid residues present in the precursor enzyme corresponding to position +210 in combination with one or more the following radicals: +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, wherein the numbered Position of course occurring subtilisin of Bacillus amyloliquefaciens or equivalent amino acid residues in other carbonyl hydrolases or subtilisins, such as Bacillus lentus subtilisin, corresponds (simultaneously pending Patent Application US Serial No. 60 / 048,550, filed June 4 1997, and PCT International Application Serial No. PCT / IB98 / 00853).

Also suitable according to the invention are proteases, described in the patent applications EP 251 446 and WO 91/06637, protease BLAP ^® described in WO91 / 02792 and their variants described in WO 95/23221.

As well is a protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A at Novo, with activity possible in the upper pH range.

Enzymatic detergents comprising a protease, one or more other enzymes and a reversible protease inhibitor are described in WO 92/03529 A to Novo. If desired, a protease with reduced adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble. A recombinant trypsin-like protease for detergent useful herein is described in WO 94/25583 to Novo. Other suitable proteases are in EP 516 200 described by Unilever.

Particularly useful proteases are described in PCT publications: WO 95/30010, WO 95/30011 and WO 95/29979. Suitable proteases are as ESPERASE® ^®, Alcalase ^®, DURAZYM ^®, SAVINASE ^®, Everlase® ^® and Kannase® ^® all from Novo Nordisk A / S, Denmark, and as MAXATASE ^®, MAXACAL ^®, PROPERASE® ^® and MAXAPEM ^® all from Genencor International (formerly Gist-Brocades, The Netherlands) commercially available.

Such Proteolytic enzymes, if present, are incorporated in the cleaning compositions of the present invention in a concentration of 0.0001% by weight to 2 wt .-%, preferably from 0.001 wt .-% to 0.2 wt .-%, more preferably from 0.005 wt .-% to 0.1 wt .-% pure enzyme, based on the weight of the composition, incorporated.

Amylases (α and / or β) can be included to remove carbohydrate-based stains. WO94 / 02597 describes cleaning compositions containing amylase mutants. See also WO95 / 10603. Other amylases known for use in cleaning compositions include both α- and β-amylases. α-Amylases are known in the art and include those described in U.S. Patent 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 No. 1,296,839 (Novo). Other suitable amylases are stability-enhanced amylases described in WO94 / 18314 and WO96 / 05295, Genencor, and amylase variants with additional modification in the immediate starting material, available from Novo Nordisk A / S, disclosed in WO 95/10603. Also suitable are amylases which are in EP 277 216 are described.

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. WO95 / 26397 describes other suitable amylases: α-amylases, characterized in that they are in a temperature range of 25 ° C to 55 ° C and at a pH in the range of 8 to 10, as measured by the Phadebas ^® -α -Amylase activity approach, have a specific activity that is at least 25% higher than the specific activity of Termamyl ^® . Suitable variants of the abovementioned enzymes are those described in WO96 / 23873 (Novo Nordisk). Other amylolytic enzymes having improved properties in terms of activity level and the combination of thermal stability and a higher level of activity are described in WO95 / 35382.

Such Amylolytic enzymes, if present, are incorporated in the cleaning compositions of the present invention in a concentration of 0.0001 wt .-% to 2 wt .-%, preferably from 0.00018% by weight to 0.06% by weight, more preferably from 0.00024% by weight to 0.048% by weight of pure enzyme, based on the weight of the composition, incorporated.

The mentioned above Enzymes can have any suitable origin, such as plants, animals, bacteria, Mushrooms and yeasts. You can furthermore mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.) origin. It can be purified or non-purified forms of these enzymes are used. nowadays It is common, wild-type enzymes using protein / genetic engineering techniques to modify their Power efficiency in the laundry detergent and / or fabric care compositions of the invention. For example, you can The variants should be designed so that the compatibility of the enzyme in terms of generally more common Components of such compositions is increased. As an alternative can the variant should be designed so that the optimum pH, bleach or chelant stability, catalytic activity and the like of the enzyme variant on the particular cleaning application is tailored.

Especially In the case of bleach stability, attention should be paid to amino acids that are sensitive for oxidation are, and for the surfactant compatibility on surface use judge. The isoelectric point of such enzymes can be determined by the Substitution of some amino acids used are changed, e.g. can one Increase of the isoelectric point help the compatibility with anionic To improve surfactants. The stability of the enzymes can be improved by the Creation of e.g. additional salt bridges and enforcing calcium binding sites to increase chelant stability be improved.

These optional cleansing enzymes, if any, are usually in the cleansing compositions in concentrations of 0.0001 to 2 wt .-% of pure enzyme, based on the cleaning composition. The enzymes can be considered as separate individual ingredients (prills, granules, stabilized liquids, etc., which contain an enzyme) or as mixtures of two or several enzymes (eg cogranules) are added.

Other suitable detergent ingredients that may be added are Enzyme oxidation scavengers. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.

A number of enzyme materials and adjuvants for their incorporation into synthetic detergent compositions are also described in WO 93/07263 and WO 93/07260, Genencor International, WO 89/08694 and in US Pat US 3,553,139.5 , January 1971, to McCarty et al. Enzymes are further disclosed in U.S. Patent No. 4,101,457 and U.S. Patent No. 4,507,219. Enzyme materials suitable for liquid detergent formulations and their incorporation into such formulations are disclosed in U.S. Patent No. 4,261,868.

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

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

• (i) α-Amylase, die dadurch gekennzeichnet ist, dass sie in einem Temperaturbereich von 25 °C bis 55 °C und bei einem pH-Wert im Bereich von 8 bis 10, gemessen durch den Phadebas^® α-Amylaseaktivitätsansatz, eine spezifische Aktivität aufweist, die mindestens 25 % höher ist als die spezifische Aktivität von Termamyl^®; und/oder
• (ii) α-Amylase gemäß (i), die die in SEQ-ID Nr. 1 gezeigte Aminosäure-Sequenz umfasst, oder eine α-Amylase, die zu mindestens 80 % mit der in SEQ-ID Nr. 1 gezeigten Aminosäure-Sequenz homolog ist; und/oder
• (iii) α-Amylase gemäß (i), die die in SEQ-ID Nr. 2 gezeigte Aminosäure-Sequenz umfasst, oder eine α-Amylase, die zu mindestens 80 % mit der in SEQ-ID Nr. 2 gezeigten Aminosäure-Sequenz homolog ist; und/oder
• (iv) α-Amylase gemäß (i), die den folgenden Aminosäure-Sequenz-N-Terminal umfasst: His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp (SEQ-ID Nr. 3), oder eine α-Amylase, die zu mindestens 80 % mit der gezeigten Aminosäure-Sequenz (SEQ-ID Nr. 3) in dem N-Terminal homolog ist; und/oder
• (v) α-Amylase gemäß (i–iv), worin die α-Amylase aus einer alkalophilen Bacillus-Art gewonnen werden kann; und/oder
• (vi) α-Amylase gemäß (v), worin die Amylase aus einem der Stämme NCIB 12289, NCIB 12512, NCIB 12513 und DSM 935 gewonnen werden kann; und/oder
• (vii) α-Amylase mit positiver immunologischer Kreuzreaktivität mit Antikörpern, die gegen eine α-Amylase mit einer Aminosäure-Sequenz, die SEQ-ID Nr. 1, ID Nr. 2 bzw. ID Nr. 3 entspricht, gezüchtet wurden; und/oder
• (viii) Variante einer Stamm-α-Amylase, worin die Stamm-α-Amylase (1) eine der in SEQ-ID Nr. 1, ID Nr. 2 bzw. ID Nr. 4 gezeigten Aminosäure-Sequenzen aufweist oder (2) mindestens 80 % Homologie mit einer oder mehreren der Aminosäure-Sequenzen zeigt und/oder immunologische Kreuzreaktivität mit einem Antikörper, der gegen eine α-Amylase mit einer der Aminosäure-Sequenzen gezüchtet wurde, zeigt und/oder durch eine DNA-Sequenz kodiert ist, die mit der gleichen Probe hybridisiert wie eine DNA-Sequenz, die eine α-Amylase mit einer der Aminosäure-Sequenzen kodiert, wobei in diesen Varianten: (A) mindestens ein Aminosäurerest der Stamm-α-Amylase entfernt wurde und/oder (B) mindestens ein Aminosäurerest der Stamm-α-Amylase durch einen anderen Aminosäurerest ersetzt wurde und/oder (C) mindestens ein Aminosäurerest in die Stamm-α-Amylase eingeführt wurde, wobei die Variante eine α-Amylaseaktivität aufweist und mindestens eine der folgenden Eigenschaften bezüglich der Stamm-α-Amylase zeigt: erhöhte Thermostabilität; erhöhte Stabilität gegenüber Oxidation; verringerte Ca-Ionenabhängigkeit; erhöhte Stabilität und/oder α-amylolytische Aktivität bei neutralen bis verhältnismäßig hohen pH-Werten; erhöhte α-amylolytische Aktivität bei verhältnismäßig hoher Temperatur; und Anstieg oder Abfallen des isoelektrischen Punktes (pI), um den pI-Wert für die α-Amylasevariante besser an den pH des Mediums anzupassen.

Suitable α-amylase variants for use in the present invention include, but are not limited to, the following α-amylases:

• (i) α-amylase, which is characterized in that it in a temperature range from 25 ° C to 55 ° C and measured by the Phadebas ^® α-Amylaseaktivitätsansatz, a specific activity at a pH value ranging from 8 to 10, having at least 25% higher than the specific activity of Termamyl ^®; and or
• (ii) α-amylase according to (i) comprising the amino acid sequence shown in SEQ ID NO: 1, or an α-amylase having at least 80% of the amino acid sequence shown in SEQ ID NO: 1 is homologous; and or
• (iii) α-amylase according to (i) comprising the amino acid sequence shown in SEQ ID NO: 2, or an α-amylase having at least 80% of the amino acid sequence shown in SEQ ID NO: 2 is homologous; and or
• (iv) α-amylase according to (i) comprising the following amino acid sequence N-terminal: His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu -Trp-Tyr-Leu-Pro-Asn-Asp (SEQ ID NO: 3), or an α-amylase containing at least 80% of the shown amino acid sequence (SEQ ID NO: 3) in the N- Terminal is homologous; and or
• (v) α-amylase according to (i-iv), wherein the α-amylase can be obtained from an alkalophilic Bacillus species; and or
• (vi) α-amylase according to (v), wherein the amylase can be obtained from any of NCIB 12289, NCIB 12512, NCIB 12513 and DSM 935; and or
• (vii) α-amylase having positive immunological cross-reactivity with antibodies raised against an α-amylase having an amino acid sequence corresponding to SEQ ID NO: 1, ID NO: 2 and ID NO: 3, respectively; and or
• (viii) variant of a parent α-amylase wherein the parent α-amylase (1) has any one of the amino acid sequences shown in SEQ ID NO: 1, ID NO: 2 and ID NO: 4, respectively, or (2) at least 80% homology with one or more of the amino acid sequences and / or immunological cross-reactivity with an antibody raised against an α-amylase with one of the amino acid sequences, and / or encoded by a DNA sequence hybridized with the same sample as a DNA sequence encoding an α-amylase with one of the amino acid sequences, wherein in these variants: (A) at least one amino acid residue of the parent α-amylase has been removed and / or (B) at least an amino acid residue of the parent α-amylase has been replaced by another amino acid residue and / or (C) at least one amino acid residue has been introduced into the parent α-amylase, the variant having an α-amylase activity and at least one of the following characteristics regarding the parent α-amylase shows: increased thermostability; increased stability against oxidation; reduced Ca ion dependence; increased stability and / or α-amylolytic activity at neutral to relatively high pHs; increased α-amylolytic activity at a relatively high temperature; and increasing or decreasing the isoelectric point (pI) to better match the pI value for the α-amylase variant with the pH of the medium.

One Polypeptide is considered to be X% homologous to the parent amylase, if a comparison of the corresponding amino acid sequences performed by Algorithms such as that of Lipman and Pearson in Science 227, 1985, p. 1435 described a match disclosed by X%.

in the For the purposes of the present invention, the term "win from "not just one Denote amylase produced by a Bacillus strain but also an amylase encoded by a DNA sequence which isolated from such a Bacillus strain and in a host organism, which is transformed with this DNA sequence is produced.

enzyme stabilizers

Enzymes for use in detergents can be stabilized by various methods. Enzyme stabilization methods are described in U.S. Patent No. 3,600,319, EP 199,405 and EP 200,586 disclosed and exemplified. For example, enzyme stabilization systems are also available in US 3,519,570 described. A useful Bacillus, sp. AC 13, which provides proteases, xylanases and cellulases, is described in WO 9401532. The enzymes employed herein can be stabilized in the final compositions by the presence of water-soluble calcium and / or magnesium ion sources which provide such ions to the enzymes. Suitable enzyme stabilizers and use concentrations are described in US Pat. No. 5,705,464, 5,710,115 and 5,576,282.

following is a non-limiting example for the preparation of a bleach catalyst that stains in the absence a peroxide source effectively bleaches.

EXAMPLE 1 Synthesis of 5,12-dimethyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane manganese (II) chloride having the formula:

und wird in 100%iger Ausbeute (6,0 g) gewonnen.Into a 250 ml three-neck round bottom flask equipped with a thermometer, nitrogen inlet and magnetic stirrer is added N, N'-bis (2-aminoethyl) -1,3-propanediamine (5.00 g, 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% in water) is added dropwise with stirring. Upon completion of the addition, the solution is concentrated under reduced pressure to give a clear, colorless oil. The isolated oil has the formula 1:

and is recovered in 100% yield (6.0 g).

und wird in 100%iger Ausbeute (7,0 g) gewonnen.Cyclic amine 1 (6.0 g) is suspended in acetonitrile (100 ml). Potassium carbonate (25 g) and 1,3-Pro Pandiol dinositate (12.61 g, 32.8 mmol) is added. The solution is stirred vigorously at RT overnight. The reaction mixture is then warmed to 70 ° C and filtered hot with glass fiber filter paper and vacuum filtration. The resulting solid is washed with acetonitrile (100 ml). The acetonitrile filtrate is concentrated under reduced pressure to give a light green oil of Formula 2:

and is recovered in 100% yield (7.0 g).

und wird in ungefähr 85%iger Ausbeute gewonnen.The tetraamine 2 (7.0 g) is dissolved in acetonitrile (150 ml). Methyl sulfate (2.5 equiv.) Is added, the reaction heated to 65 ° C and stirred for 9 days. The solvent is removed under reduced pressure to obtain a brown oil of formula 3:

and is recovered in approximately 85% yield.

als ein Öl zu ergeben, in 95%iger Ausbeute (5,2 g) nach Destillation.Distilled water (25 mL) and potassium carbonate (13.8 g) are added to a 250 mL round bottom flask. Absolute ethanol (75 ml) is added and the resulting two-phase solution is stirred and heated to 60 ° C with an oil bath. Sodium tetrahydridoborate (1.60 g, 42.3 mmol) and 3 (10.0 g, 21.1 mmol) were added to the solution. The reaction mixture 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 material is dissolved in 5N KOH (5 mL) and extracted with toluene (2 × 50 mL). The toluene is removed under reduced pressure to give 5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane having the formula:

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

Into a flame-dried, 12 liter, 3-neck round bottom flask equipped with a heating mantle, stir bar, and oven-dried condenser is added anhydrous acetonitrile (5 liters) to give 5,12-dimethyl-1,5,8,12-tetra-azae. bicyclo [6.6.2] hexadecane (484 gm, 1.9 mol). The milky white Suspen The mixture is placed under a 10mm vacuum until the suspension boils and then the reaction vessel is purged with argon. This degassing is carried out 7 times. After the degassing is complete, manganese (II) chloride (228 gm, 1.81 mol) is added. After refluxing for 4 hours with vigorous stirring, the suspension is filtered immediately through glass filter paper. The solvent is removed from the filtrate under reduced pressure at 45 ° C to obtain a solid. The solid is then suspended in 500 ml of toluene and the supernatant decanted. This wash is repeated until the supernatant is colorless (typically 7 times with approximately 7 x 500 ml of toluene). The remaining solid is dried in vacuo to give 575 g (84%) of 5,12-dimethyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane manganese (II) chloride. A second product recovery is obtained by further washing of the solid material and subsequent treatment of the resulting solid in the same way. The total yield is 636 g (93%).

The following are not restrictive Examples of liquid laundry heavy duty detergent compositions according to the invention (HDL).

TABLE I

• 1. 5,12-Dimethyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane-manganese (II) chloride.
• 2. Butylated hydroxytoluene.
• 3. potassium bisulfite.
• 4. Potassium sulfite.
• 5. PEI 189 E15-18 according to the US patent No. 4,597,898, Vander Meer, issued July 1, 1986.
• 6. Dirt-repellent according to the US patent No. 4,702,857, Gosselink, issued October 27, 1987.
• 7. Dirt repellent according to the US patent No. 4,968,451, Scheibel et al., Issued November 6, 1990.

TABLE II

• 1. 5,12-Dimethyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane-manganese (II) chloride.
• 2. Butylated hydroxytoluene.
• 3. potassium bisulfite.
• 4. Potassium sulfite.
• 5. PEI 189 E15-18 according to the US patent No. 4,597,898, Vander Meer, issued July 1, 1986.
• 6. Dirt-repellent according to the US patent No. 4,702,857, Gosselink, issued October 27, 1987.
• 7. Dirt repellent according to the US patent No. 4,968,451, Scheibel et al., Issued November 6, 1990.

Claims (11)

A bleaching composition comprising: A) a catalytically effective amount of a transition metal bleach catalyst, a complex of a transition metal and a cross-linked one macropolycyclic ligand; B) an effective amount of a Stabilizing agent, wherein the agent is selected from i) 0.01 to 10% by weight of one or more antioxidants; ii) From 0.001 to 1% by weight of one or more reducing agents; iii) and mixtures thereof; and C) to other parts carrier and other additional components; with the proviso that the composition in the Essentially free of any organic or inorganic peroxygen compounds wherein is substantially free of any organic or inorganic Peroxygen compounds means that any amounts of organic or inorganic peroxygen compounds that are present can, so are that they under typical conditions of use no additional bleaching activity deploy to stains. The composition of claim 1, wherein the transition metal bleach catalyst comprises: i) 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), Ni (I), Ni (II), Ni (III), Cu (I), Cu (II) Cu (III), Cr (II), Cr (III), Cr (IV), Cr (V), Cr (VI), V (III), 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) and mixtures thereof; and ii) a cross-bridged macropolycyclic ligand coordinated to the same transition metal by four or five donor atoms, the ligand comprising: a) an organic macrocyclic ring containing four or more donor atoms formed by covalent bonds of 2 or 3 non-donor atoms wherein two to five of these donor atoms are coordinated to the same transition metal atom in the complex; b) a cross-linked chain covalently linking at least two non-adjacent donor atoms of the organic macrocyclic ring, wherein the covalently bonded, non-adjacent donor atoms are bridgehead donor atoms coordinated to the same transition metal in the complex, and wherein the chain is substituted with the Transverse bridges comprising 2 to about 10 atoms; c) optionally one or more non-macropolycyclic (n) ligands, preferably selected from the group consisting of H ₂ O, ROH, NR _3, RCN, OH ^-, OOH ^-, RS ^-, RO ^-, RCOO ^-, OCN ^-, SCN ^-, N ₃ ^-, CN ^-, F ^-, Cl ^-, Br ^-, I ^-, O ₂ ^-, NO ₃ ^-, NO ₂ ^-, SO ₄ ^2-, SO ₃ ^2-, PO ₄ ^3-, organic Phosphates, organic phosphonates, organic sulfates, organic sulfonates and aromatic N donors such as pyridines, pyrazines, pyrazoles, imidazoles, benzimidazoles, pyrimidines, triazoles and thiazoles, wherein R is H, optionally substituted alkyl, optionally substituted aryl. A composition according to claim 1 or 2, wherein the organic macrocyclic ring comprises at least four donor atoms, which are N, the donor atoms being formed by covalent bonds of 2 to 4 non-donor atoms are separated, with the donor atoms coordinatively to the same transition metal atom are attached. The composition of claim 1 which is at least about 1 ppb a transition metal bleach catalyst includes. The composition of claim 1, wherein the transition metal bleach catalyst 5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) chloride is. A composition according to claim 1, wherein the stabilizing agent an antioxidant selected from the group consisting from 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, mixtures of 2- and 3-tert-butyl-4-methoxyphenol, 5-hydroxy-2,2,4,6,7-pentamethyl-2,3-dihydro-1-benzofuran-3-one, 5-hydroxy-3-methylene-2,2,4,6,7-pentamethyl 2,3-dihydrobenzofuran, 5-Benzyloxy-3-hydroxymethyl-2,2,4,6,7-pentamethyl-2,3-dihydro-1-benzofuran, 3-hydroxymethyl-5-methoxy-2,2,4,6,7-pentamethyl-2,3-dihydro-1-benzofuran and mixtures thereof. A composition according to claim 1, wherein the stabilizing agent a reducing agent is selected from the group consisting of sodium sulfate, potassium sulfite and mixtures from that. A liquid laundry, laundry pre-treatment or pretreatment 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; b) an effective amount of a stabilizing agent, wherein the agent is selected from i) 0.01 to 10% by weight of one or more antioxidants; ii) from 0.001 to 1% by weight of one or more reducing agents; iii) and mixtures thereof; and (c) to other parts, carriers and other ancillary components; with the proviso that the composition is substantially free of any organic or inorganic peroxygen compounds wherein substantially free of any organic or inorganic peroxygen compounds means that any amounts of organic or inorganic peroxygen compounds which may be present are such as to be present in the present invention typical usage conditions do not provide additional bleach activity on stains. A composition according to claim 8, wherein the catalyst comprises: i) 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), Ni (I), Ni (II), Ni (III), Cu (I), Cu (II), Cu ( III), Cr (II), Cr (III), Cr (IV), Cr (V), Cr (VI), V (III), 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), and ii) a cross-bridged macropolycyclic ligand wherein the ligand is selected from the group consisting of: a) a cross-bridged macropolycyclic ligand of formula (I) having a denticity of 4 or 5:

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

c) the cross-bridged macropolycyclic ligand of formula (III) having a denticity of 6 or 7:

wherein each E unit represents the radical having the formula: (CR _n ) _a -X- (CR _n ) _{a '} wherein X is selected from the group consisting of oxygen, sulfur, -NR-, phosphorus, or X is a covalent bond, wherein E has the formula: (CR _n ) _a - (CR _n ) _{a '} for each E unit, the sum of a + a 'is independently selected from 1 to 5; each G unit is a (CR _n ) _b radical; each R moiety is independently selected from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl, and heteroaryl, or two or more R moieties are covalently linked to form an aromatic, heteroaromatic, or cycloalkyl or heterocycloalkyl ring; each D unit is a donor atom independently selected from the group consisting of nitrogen, oxygen, sulfur and phosphorus, and at least two atoms comprising D units are bridgehead donor atoms coordinated to the transition metal; B units are a carbon atom, a D unit or a cycloalkyl ring or a heterocyclic ring; each n is an integer independently selected from 1 and 2, which completes the valency of the carbon atoms to which the R moieties are covalently bonded; each n 'is an integer independently selected from 0 and 1, which completes the valency of the D donor atom to which the R moieties are covalently bonded; each n '' is an integer independently selected from 0, 1 and 2, which completes the valency of the B atoms to which the R moieties are covalently bonded; a and a 'are each an integer independently selected from 0 to 5, the sum of all a + a' values in the ligand of formula (I) being in the range of about 8 to about 12; the sum of all a + a 'values in the ligand of formula (II) is in the range of about 10 to about 15 and the sum of all a + a' values in the ligand of formula (III) is in the range of about 12 to is 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 ) _b residues covalently linking any of the D atoms to the B atom is absent as long as at least two (CR _n ) _b covalently bind two of the D donor atoms to the B atom in the formula, and the sum of all b indices ranges from about 2 to about 5, and d) optionally one or more macropolycyclic ligands. The composition of claim 9, wherein the catalyst comprises a non macropolycyclic ligand selected from the group consisting of H ₂ O, ROH, NR _3, RCN, OH ^-, OOH ^-, RS ^-, RO ^-, RCOO ^-, OCN ^-, SCN ^-, N ₃ ^-, CN ^-, F ^-, Cl ^-, Br ^-, I ^-, O ₂ ^-, NO ₃ ^-, NO ₂ ^-, SO ₄ ^2-, SO ₃ ^2-, PO ₄ ^3- organic phosphates, organic phosphonates, organic sulfates, organic sulfonates and aromatic N-donors such as pyridines, pyrazines, pyrazoles, imidazoles, benzimidazoles, pyrimidines, triazoles and thiazoles; wherein R is H, alkyl which is optionally substituted, and aryl which is optionally substituted. A process for bleaching stains and stains on fabrics, the process comprising the step of contacting textile fabric requiring cleaning with an aqueous or nonaqueous solution containing a composition comprising: (a) a catalytically active An amount of a transition metal bleach catalyst which is a complex of a transition metal and a cross-bridged macropolycyclic ligand; b) an effective amount of a stabilizing agent, wherein the agent is selected from i) 0.01 to 10% by weight of one or more antioxidants; ii) from 0.001 to 1% by weight of one or more reducing agents; iii) and mixtures thereof; and C) to other parts of vehicles and other additional components; with the proviso that the concentration of the transition metal bleach catalyst in the aqueous solution is at least 0.01 ppb and the composition is substantially free of any organic or inorganic peroxygen compounds in which substantially free of any organic or inorganic peroxygen compounds is used organic or inorganic peroxygen compounds that may be present are such that they do not provide additional bleaching activity to stains under typical conditions of use.