KR100453614B1 - Stabilized bleach compositions and a bleach method using the same - Google Patents

Abstract

The present invention

(A) a transition metal bleach catalyst which is a complex of a transition metal and a crosslinked bridged macropolycyclic ligand, for example 5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6. 2] catalytically effective amount of hexadecane manganese (II) chloride;

(B) an effective amount of stabilizer selected from the group consisting of (i) at least one antioxidant, (ii) at least one reducing agent and (iii) mixtures thereof, and

(C) comprises a residual amount of carrier and other accessory ingredients,

However, the present invention relates to a detergent composition for bleaching, preimpregnation, pretreatment and laundry, which is substantially free of organic or inorganic peroxygen compounds.

Formula a

Description

Stabilized bleach compositions and a bleach method using the same

Bleaching fabrics is essentially exposing contaminated or stained fabrics to chemical reactions to remove dirt or stains. At one time, bleaching was associated with exposing the fabric to hypochlorite solution. Thus, fabrics colored or dyed with sensitive pigments could not be treated with bleach. For the consumer, manufacturers have developed various types of bleaching systems, in particular peroxygen bleaching systems which typically include hydrogen peroxide sources and bleach activators. This combination of hydrogen peroxide source and bleach activator plays a dominant role in effective and safe bleaching compositions. Effective examples of such peroxygen bleaching systems use perborate (peroxygen source) and nonanoyloxybenzene sulfonate (activator).

In order to improve bleaching performance and to develop a bleaching system that is safe for all forms of dyed or colored fabrics, especially silk, polyester blends, cotton and nylon, manufacturers have used new methods of forming activated oxygen as well as peroxygen bleaching. The system has been continuously developed.

However, there is a continuing need in the art for stable bleaching systems that effectively bleach fabrics without the use of reactive chemicals such as peroxides, sources of peroxides and / or mixtures thereof. Such stable bleaching systems will include transition metal catalysts that do not degrade their effects due to the instability of the catalyst for post-oxidation and / or post-reduction formulation.

Summary of the Invention

The present invention has surprisingly found that a bleaching system comprising a transition metal catalyst capable of bleaching dirt and stains in the absence of a hydrogen peroxide source or other peroxy bleach can be successfully stabilized from unnecessary decomposition of the transition metal catalyst. Meets the above-mentioned needs in that respect. That is, surprisingly, it has been found that the addition of an effective amount of antioxidant and / or free radical scavenger or reducing agent can stabilize the hydrogen peroxide free bleaching system.

The first aspect of the invention

(A) a catalytically effective amount of a transition metal bleach catalyst, which is a complex of a transition metal and a crosslinked bridged macropolycyclic ligand;

(B) an effective amount of stabilizer selected from the group consisting of (i) at least one antioxidant, (ii) at least one reducing agent and (iii) mixtures thereof, and

(C) comprises a residual amount of carrier and other accessory ingredients,

However, it relates to a stabilized bleaching composition that is substantially free of organic or inorganic peroxygen compounds.

The present invention also provides for fabrics that need to be cleaned and / or bleached,

Substantially free of peroxy compounds,

(a) a catalytically effective amount of a transition metal bleach catalyst that is a complex of a transition metal and a crosslinked bridged macropolycyclic ligand;

an effective amount of stabilizer selected from the group consisting of (b) (i) at least one antioxidant, (ii) at least one reducing agent, and (iii) mixtures thereof, and

(c) comprises a residual amount of carrier and other accessory ingredients,

Provided that the filth adheres to the fabric, including contacting with an aqueous solution containing a composition substantially free of organic or inorganic peroxygen compounds, wherein the concentration of the transition metal bleach catalyst in the aqueous solution is at least about 0.01 ppb. A method of cleaning and / or bleaching stains.

The compositions and methods of the present invention are suitable for cleaning / bleaching surfaces for which stains must be removed. For example, hard surface detergents and automatic dishwashing compositions may use the bleaching catalyst of the present invention in articles that are substantially free of organic or inorganic peroxygen compounds.

These and other objects, features and advantages will become apparent to those skilled in the art from the following detailed description of the invention and the appended claims.

All percentages, ratios, and ratios herein are by weight unless otherwise indicated. All temperatures are in degrees Celsius unless otherwise noted. All documents cited are incorporated by reference in the relevant part of this application.

The present invention relates to a stabilized bleaching and cleaning composition comprising a catalytically effective amount of a transition metal bleaching catalyst that is a complex of a transition metal and a crosslinked bridged macropolycyclic ligand and an antioxidant or reducing agent used to stabilize the catalyst. The present invention also relates to a method of bleaching / cleaning fabrics with a catalytically effective amount of a stable transition metal bleaching catalyst in the absence of substantially organic or inorganic peroxygen compounds or precursors thereof.

The present invention relates to the surprising finding that transition metal catalysts capable of bleaching dirt and stains without the addition of peroxygen bleach can be properly stabilized by adding one or more stabilizers. Stabilizers suitable for use in the present invention are present at different levels depending on the concentration of the blend, in particular liquids, solids and gels, and the transition metals present.

Absence of Peroxygen Source

The compositions of the present invention as well as methods for cleaning and / or bleaching fabrics using the compositions of the present invention are substantially free of peroxygen sources such as hydrogen peroxide, peroxy acid and the like. The compositions of the present invention require only the effective amount of catalyst described below present for effective bleaching. For the purposes of the present invention, the term "substantially free" refers to "a level necessary for a manufacturer to effectively bleach a peroxygen compound or peroxygen source in the absence of a transition metal catalyst or in the presence of a transition metal catalyst as defined herein. Not included in the composition to the level necessary to increase the bleaching effect. " Thus, as further described below, effective bleaching of the stain can be achieved by simply adding an aqueous or non-aqueous solution of the catalyst described herein to the stained fabric, preferably the fabric is present in the aqueous solution when in contact with the catalyst. do. However, it is recognized that peroxygen sources can be unknowingly introduced into and / or formed in the product due to factors beyond the manufacturer's control, in particular the source of the product raw material, unnecessary decomposition of one or more components. The compositions of the present invention do not require any source of peroxygen, but their presence in trace amounts will not affect the performance of the bleaching compositions described herein.

The manufacturer can typically include a small amount of hydrogen peroxide source in the composition to stabilize the enzyme, for example adding a small amount of perborate. However, this amount of perborate is usually too minor to affect the bleaching performance of the compositions of the present invention. If the manufacturer adds traces of oxidant or other peroxide source to stabilize the auxiliary component, for the purposes of the present invention, these compositions are also defined above if they do not provide additional bleaching activity to the stain under ordinary conditions of use. As defined as "substantially free". For example, a composition that is "substantially free" may comprise a source of peroxygen in an amount substantially the same as when the effect of the catalyst is absent. For the purposes of the present invention, a composition comprising less than 0.1%, preferably less than 0.01% of a primary oxidant (eg, preformed peracid) or hydrogen peroxide source is "substantially free" as further defined herein. Is considered. In addition, a wash liquor, laundry wash water, pre-impregnation bath, or other fabric or surface cleaning solution in which the catalyst of the present invention is used and preformed or otherwise comprising less than 0.001% by weight of a peroxide source formed by itself may be It is defined herein as "substantially free". That is, if a bleach of fabric is bleached using the catalyst of the present invention, or a hard surface or dish is washed / bleached and the solution containing the catalyst contains a peroxygen source at a concentration of less than 0.001%, the solution is peroxygenated. It is defined herein as "substantially free" of a source.

Bleach catalyst

The composition of the present invention comprises an effective amount of bleach catalyst. The term "effective amount" refers to the amount of transition metal bleaching catalyst present in the composition of the present invention or present during use according to the method of the present invention, that is, to which the composition or method of the invention It is defined as an amount sufficient to at least partially oxidize the material. Typically, the materials to be oxidized are unnecessary materials, in particular food and beverage stains, oil / oil stains, body dirts on fabrics, but the present invention is not limited thereto. Oxidation in the absence of peroxygen sources has various applications, and the present invention is not limited to bleaching and / or cleaning of fabrics. For example, automated dishwashing compositions are one aspect of the present invention, wherein bleaching the stain using compositions and / or solutions that are "substantially free" of a peroxygen source is part of the present invention. The same also applies to solutions comprising hard surface cleaning compositions and hard surface cleaning compositions that are "substantially free" of peroxygen sources.

Preferably, the composition of the present invention comprises from about 1 ppb (0.0000001%) to about 99.9%, more preferably from about 100 ppb (0.00001%) to about 50% of the transition metal catalyst as described below based on the weight of the composition And even more preferably from about 500 ppm (0.00005%) to about 5%, even more preferably from about 1 ppm (0.001%) to about 500 ppm (0.05%).

In the broadest aspect, the transition metal bleaching catalyst of the present invention

(i) 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) , Transition metals selected from the group consisting of Fe (IV), Cr (II), Cr (III), Cr (IV), Cr (V), Cr (VI), and mixtures thereof

(ii) (a) at least four donor atoms separated from each other by covalent bonds of two or three non-donor atoms [preferably at least three of these donor atoms, more preferably at least four are N Organic macrocycle rings containing 2 to 5 (preferably 3 to 4, more preferably 4) of these donor atoms are coordinated to the same transition metal atom in the complex;

(b) 2 to about 10 crosslinked bridged chains which covalently bond two or more non-contiguous donor atoms of the organic macrocycle ring (preferably, the crosslinked bridged chain is two, three or four Selected from 4 to 6 non-donor atoms with non-donor atoms, and additional donor atoms, wherein covalently bonded nonadjacent donor atoms are bridgehead donor atoms coordinated to the same transition metal in the complex ;

(c) optionally, preferably 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-, Groups consisting of organic phosphates, organic phosphonates, organic sulfates, organic sulfonates, and aromatic N donors including pyridine, pyrazine, pyrazole, imidazole, benzimidazole, pyrimidine, triazole and thiazole , R is H, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl) Crosslinked bridged macrocyclic ligands that are coordinated to the same transition metal by four to five donor atoms, including one or more non-macropolycyclic ligands.

Preferred crosslinked bridged macropolycyclic ligands are

(a) crosslinked bridged macropolycyclic ligands of formula (I) having four or five denticities;

(b) crosslinked bridged macropolycyclic ligands of formula II having 5 or 6 protuberances, and

(c) is selected from the group consisting of crosslinked bridged macropolycyclic ligands of formula III having 6 or 7 protrusions:

In Chemical Formulas I to III,

Each E unit is a residue of formula (CR _n ) _a -X- (CR _n ) _{a '} wherein X is selected from the group consisting of oxygen, sulfur, -NR- and phosphorus, or E is selected from formula (CR _n ) _a -(CR _n ) is a covalent bond to represent a residue of _{a '} ), and the sum of a + a' in each E unit is independently selected from 1 to 5,

Each G unit is a residue (CR _n ) _b ,

Each R unit is independently selected from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl and heteroaryl, or two or more R units are covalently bonded to form an aromatic, heteroaromatic, cycloalkyl or heterocycloalkyl ring and,

Each D unit is a donor atom independently selected from the group consisting of nitrogen, oxygen, sulfur and phosphorus, at least two atoms comprising a D unit are bridgehead donor atoms coordinated to a transition metal,

The B unit is a carbon atom, a D unit, or a cycloalkyl or heterocyclic ring,

n is an integer independently selected from 1 and 2, each of which meets the valence of the carbon atom to which the R unit is covalently bonded,

n 'is an integer independently selected from 0 and 1, each of which meets the valence of the D donor atom to which the R residue is covalently bonded,

n "is an integer independently selected from 0, 1 and 2, each of which meets the valence of the B atom to which the R residue is covalently bonded,

a and a 'are each independently an integer selected from 0 to 5, wherein the sum of all a + a' values in the ligand of formula I is in the range of about 8 to about 12, and all a + a in the ligand of formula II 'The sum of the values 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 about 18),

b is each an integer independently selected from 0 to 9, or in the formula, at least one covalently linking D to a B atom so long as at least two (CR _n ) _b covalently bonds two D donor atoms to a B atom (CR _n ) _b residues are absent and the sum of all b indices is in the range of about 2 to about 5.

Further descriptions of the bleach catalysts of the present invention are disclosed in WO 98/39406 A1, published September 11, 1998, WO 98/39098, published September 11, 1998, all of which are incorporated herein by reference. A1 and WO 98/39335 A1 published September 11, 1998.

The nomenclature used throughout this specification to describe transition metal catalysts is the same as the nomenclature used in the references cited above. However, the chemical names of one or more ligands described herein may differ from the chemical names designated under the principles of International Pure Applied Chemistry (IUPAC). For example, the IUPAC name for 5,12-dimethyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane, which is a preferred ligand for the purposes of the present invention, is 4,11-dimethyl-1, 4,8,11-tetraaza-bicyclo [6.6.2] hexadecane.

Transition metal bleaching catalysts useful in the compositions of the present invention may more preferably include a number of novel compounds specifically designed for existing washing or cleaning as well as known compounds consistent with the definition of the present invention. Non-limiting examples of suitable catalysts according to the invention are as follows:

Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II),

Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane manganese (II),

Diaquao-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,

Diaquao-4,10-dimethyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane manganese (II) hexafluorophosphate,

Diaquao-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) tetrafluoroborate,

Diaquao-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,

Dichloro-5,12-di-n-butyl-1,5,8,12-tetraaza-bicyclo [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-tetraaza-bicyclo [6.6.2] hexadecane manganese (II),

Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane manganese (II),

Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane manganese (II),

Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane iron (II),

Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane iron (II),

Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane copper (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 cobalt (II),

Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane cobalt (II),

Dichloro-5,12-dimethyl-4-phenyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II),

Dichloro-4,10-dimethyl-3-phenyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane manganese (II),

Dichloro-5,12-dimethyl-4,9-diphenyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II),

Dichloro-4,10-dimethyl-3,8-diphenyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane manganese (II),

Dichloro-5,12-dimethyl-2,11-diphenyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II),

Dichloro-4,10-dimethyl-4,9-diphenyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane manganese (II),

Dichloro-2,4,5,9,11,12-hexamethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II),

Dichloro-2,3,5,9,10,12-hexamethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II),

Dichloro-2,2,4,5,9,9,11,12-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),

Dichloro-3,5-10,12-tetramethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II),

Dichloro-3-butyl-5,10,12-trimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II),

Dichloro-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II),

Dichloro-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane manganese (II),

Dichloro-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane iron (II),

Dichloro-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane iron (II),

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),

Chloro-10- (2-hydroxybenzyl) -4-methyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane manganese (II),

Chloro-5-methyl-12- (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,

Dichloro-5- (2-sulfato) dodecyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (III),

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 manganese (II),

Dichloro-5- (trimethylammoniopropyl) dodecyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (III) chloride,

Dichloro-5,12-dimethyl-1,4,7,10,13-pentaazabicyclo [8.5.2] heptadecane manganese (II),

Dichloro-14,20-dimethyl-1,10,14,20-tetraazatrichloro [8.6.6] docosa-3 (8), 4,6-triene manganese (II),

Dichloro-4,11-dimethyl-1,4,7,11-tetraazabicyclo [6.5.2] pentadecane manganese (II),

Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [7.6.2] heptadecane manganese (II),

Dichloro-5,13-dimethyl-1,5,9,13-tetraazabicyclo [7.7.2] heptadecane manganese (II),

Dichloro-3,10-bis (butylcarboxy) -5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II),

Diaquao-3,10-dicarboxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II),

-1,9,20,24,25- chloro -20- methyl-penta-aza-tetracyclo [7.7.7.1 ^3,7 .1 ^11,15] -3,5,7-penta Kosa 24, 11,13, 15 (25) -hexaene manganese (II) hexafluorophosphate,

Methanesulfonic phono trifluoromethyl -1,9,20,24,25- -20- methyl-penta-aza-tetracyclo [7.7.7.1 ^3,7 .1 ^11,15] -3,5,7-penta Kosa 24 , 11,13,15 (25) -hexaene manganese (II) trifluoromethanesulfonate,

Methanesulfonic phono trifluoromethyl -1,9,20,24,25- -20- methyl-penta-aza-tetracyclo [7.7.7.1 ^3,7 .1 ^11,15] -3,5,7-penta Kosa 24 , 11,13,15 (25) -hexaene iron (II) trifluoromethanesulfonate,

Chloro-5,12,17-trimethyl-1,5,8,12,17-pentaazabicyclo [6.6.5] nanodecane 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,

Dichloro-5,12,15,16-tetramethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) or

Chloro-5-methyl-12- (2'-oxybenzyl) -1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II).

Preferred complexes useful as transition metal bleaching catalysts more generally include monometallic mononuclear classes such as those exemplified above, as well as bimetallic, trimetallic or cluster classes. Monometallic mononuclear complexes are preferred. As defined herein, the monometallic transition metal bleach catalyst contains only one transition metal atom per mol of the complex. A monometallic mononuclear complex is one in which the donor atoms of the essential macrocyclic ligand are bonded to the same transition metal atom, i.e., the essential ligand does not "bridge" two or more transition metal atoms.

Stabilizer

Antioxidant

One form of preferred stabilizer according to the invention is an antioxidant. The composition of the present invention comprises an effective amount of an antioxidant, preferably about 0.01 to about 10% by weight, more preferably about 0.1 to about 5% by weight, most preferably about 0.2 to about 1% by weight. Preferably the antioxidant is a free radical scavenger.

One class of antioxidants suitable for use in the present invention is Alkylated phenols wherein R is C ₁ -C ₂₂ straight or branched alkyl, preferably methyl or branched C ₃ -C ₆ alkyl; C ₃ -C ₆ alkoxy, preferably methoxy; R ¹ is C ₃ -C ₆ branched alkyl, preferably tertiary butyl; x is 1 or 2].

Another class of antioxidants suitable for use in the present invention are Benzofuran derivatives wherein R ¹ and R ² are each independently C ₁ -C ₄ alkyl, or R ¹ and R ² together may form a C ₅ -C ₆ cyclic hydrocarbyl residue; 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, wherein A is a nitrogen containing unit, phenyl or substituted phenyl]. Preferred nitrogen containing units A include amines, pyrrolidino, piperidino, morpholino, piperazino and mixtures thereof.

Non-limiting examples of antioxidants suitable for use in the present invention include phenols, particularly 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2- and 3-3 Mixtures of tertiary butyl-4-methoxyphenol and propyl gallate, terbutylhydroquinone, benzoic acid derivatives (e.g. methoxy benzoic acid, methylbenzoic acid, dichloro benzoic acid, dimethyl benzoic acid, 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-di Hydro-benzofuran, 5-benzyloxy-3-hydroxymethyl-2,2,4,6,7-pentamethyl-2,3-dihydro-1-benzofuran, 3-hydroxymethyl-5-meth Other components including methoxy-2,2,4,6,7-pentamethyl-2,3-dihydro-1-benzofuran).

reducing agent

One form of preferred stabilizer according to the invention is a reducing agent. The composition of the present invention comprises an effective amount of at least one reducing agent, preferably about 0.001 to about 1 weight percent, more preferably about 0.01 to about 0.5 weight percent, most preferably about 0.02 to about 0.1 weight percent. Preferably, the reducing agent is an inorganic compound.

Non-limiting examples of reducing agents include sodium sulfite, potassium sulfite, ammonium sulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, potassium bisulfite, pyrosulfite salts, sodium borohydride, lithium borohydride, lithium aluminum isopro Included are compounds capable of producing sulfite ions, including oxides and mixtures thereof.

How to use

The invention also relates to a method of using a stabilized bleach catalyst without the need for a peroxygen source to clean dirt and stains from the fabric.

Accordingly, the present invention provides a fabric that needs to be cleaned,

Substantially free of peroxygen sources

(a) a catalytically effective amount of a transition metal bleach catalyst, which is a complex of a transition metal and a crosslinked bridged macropolycyclic ligand;

an effective amount of stabilizer selected from the group consisting of (b) (i) at least one antioxidant, (ii) at least one reducing agent, and (iii) mixtures thereof, and

(c) comprises a residual amount of carrier and other accessory ingredients,

Except for contacting with an aqueous solution or non-aqueous solution containing a composition substantially free of organic or inorganic peroxygen compounds, wherein the concentration of the transition metal bleach catalyst in the solution is at least about 0.01 ppb. It also relates to bleaching dirt and stains on fabrics in the absence of

The concentration of the catalyst in the solution comprising the transition metal bleach catalyst is about 1 ppb, more preferably about 10 ppb, even more preferably about 100 ppb. For example, 100 ppb (1 part per billion) is a solution containing 0.00001% by weight of catalyst. As defined herein above, a solution comprising less than 0.001% peroxygen source is a solution that is "substantially free" of organic or inorganic peroxygen compounds.

Overall, large scale bleaching itself, for example industrial or manufacturing processes, may use a high concentration catalyst, for example at least 1 ppm, to shorten the contact time of the fabric with the catalyst containing solution.

Auxiliary

Bleaching, preimpregnation, pretreatment, laundering or automatic dishwashing, or hard surface cleaning compositions of the invention, which may be granules, solids (bars), gels or liquids, further comprise one or more carriers and auxiliary components. can do.

The composition according to the invention

(a) a catalytically effective amount of a transition metal bleach catalyst that is a complex of a transition metal and a crosslinked bridged macropolycyclic ligand; And

(b) optionally from about 0.001 to about 90 weight percent of one or more dye fixatives;

(c) optionally from about 0.01 to about 50 weight percent of one or more cellulose reactive dye fixative;

(d) optionally, from about 0.01 to about 15 weight percent chlorine scavenger;

(e) optionally from about 0.005 to about 1 weight percent of one or more crystal growth inhibitors;

(f) optionally from about 0.01 to about 20 weight percent of fabric wear reducing polymer;

(g) optionally from about 1 to about 12 weight percent of one or more liquid carriers;

(h) optionally from about 0.001 to about 1 weight percent of an enzyme;

(i) optionally from about 0.01 to about 8 weight percent of a polyolefin emulsion or suspension;

(j) optionally from about 0.01 to about 0.2 weight percent of a stabilizer;

(k) optionally from about 1 to about 80 weight percent fabric softener;

(l) optionally, less than about 15 weight percent of the main solvent; And

(m) about 0.01 to 60 weight percent, preferably about 0.1 to about 30, optionally one or more surfactants selected from the group consisting of anionic, cationic, nonionic, amphoteric, zwitterionic surfactants and mixtures thereof It may include weight percent.

Surfactants

The bleaching, preimpregnating, pretreatment and laundry detergent compositions of the invention, according to embodiments, are a class selected from the group consisting of anionic, cationic, nonionic, zwitterionic, amphoteric surfactants and mixtures thereof. It may comprise about 0.01 to about 60% by weight, preferably about 0.1 to about 30% by weight detergent detergent system consisting of the above surfactant. Within each class of surfactant, more than one type of surfactant may be selected. For example, preferably in the solid (i.e. granules) and viscous semisolid (i.e. gelatinous, paste, etc.) systems of the present invention, the surfactant is preferably from about 0.1 to 60% by weight of the composition, preferably 30 It is present in weight percent or less.

Non-limiting examples of surfactants useful herein include

(a) C ₁₁ -C ₁₈ alkyl benzene sulfonates (LAS);

(b) C ₁₀ -C ₂₀ primary side chains and random alkyl sulfonates (AS);

(c) Morris, U.S. Patent No. 3,234,258, issued February 8, 1966, each of which is incorporated herein by reference, and U.S. Patent No. 5,075,041 to Lutz, issued December 24, 1991, 1994 Formula is a surfactant as described in US Pat. No. 5,349,101 to Roots et al., Issued on September 20, and US Pat. No. 5,389,277 to Prieto, issued on February 14, 1995. or C ₁₀ -C ₁₈ secondary (2,3) alkyl sulfates, wherein x and (y + 1) are integers of at least about 7, preferably at least about 9;

(d) C₁₀-C₁₈ Alkyl alkoxy sulfates (AE_xS), where x is preferably 1 to 7;

(e) C ₁₀ -C ₁₈ alkyl alkoxy carboxylates preferably comprising 1 to 5 ethoxy units;

(f) C ₁₂ -C ₁₈ alkyl ethoxylates, C ₆ -C ₁₂ alkyl phenol alkoxylates, where the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units, C ₁₂ -C ₁₈ alcohols and ethylene Oxide / propylene oxide block polymers, in particular C with Pluronic ^R ex BASF, described in US Patent No. 3,929,678 to Laughlin et al., Issued Dec. 30, 1975, incorporated herein by reference. _6- C ₁₂ alkyl phenol condensates;

(g) alkylpolysaccharides described in US Pat. No. 4,565,647 to Llenado, issued January 26, 1986, incorporated herein by reference; and

(h) US Pat. No. 5,489,393 to Conner et al., issued February 6, 1996 and Murch et al., issued October 3, 1995, incorporated herein by reference. Chemical formulas described in US Pat. No. 5,45,982 Polyhydroxy fatty acid amides wherein R ⁷ is C ₅ -C ₃₁ alkyl, R ⁸ is selected from the group consisting of hydrogen, C ₁ -C ₄ alkyl and C ₁ -C ₄ hydroxyalkyl, Q is a chain A polyhydroxyalkyl moiety having a straight-chain alkyl chain having three or more hydroxyls directly bonded to the compound, or alkoxylated derivatives thereof; Preferred alkoxy is ethoxy or propoxy and mixtures thereof; Preferred Q is derived from a reducing sugar in a reductive amination reaction, more preferably Q is a glycidyl residue; Q is more preferably -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 and R 'is hydrogen or a cyclic or aliphatic monosaccharide.

The bleaching, preimpregnation, pretreatment and laundry detergent compositions of the present invention may also contain one or more (preferably a mixture of two or more) heavy chain side chain surfactants, preferably of formula Heavy chain branched alkyl alkoxy alcohols, Heavy chain side chain alkyl sulfates and chemical formulas of The total number of carbon atoms in the heavy chain side chain alkyl alkoxy sulphate of wherein the side chain primary alkyl residues (including the R, R ¹ and R ² side chains, but not the carbon atoms comprising EO / PO alkoxy residues) is 14-20 In addition, for the aforementioned surfactant mixtures, the average total number of carbon atoms in the side chain primary alkyl moieties of the above formula is in the range of 14.5 to about 17.5 (preferably 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; Provided 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] from about 0.001 to about 100%. M is a water soluble cation and may include one or more cations such as 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 1 or more, provided that w + x + y + z is 8-14. EO and PO are each chemical formulas or Although ethyleneoxy units and propyleneoxy units of are shown, other alkoxy units, in particular 1,3-propyleneoxy, butoxy and mixtures thereof, are suitable as alkoxy units attached to heavy chain side chain alkyl moieties.

The heavy chain side chain surfactant is preferably a mixture comprising a surfactant system. Thus, when the surfactant system comprises an alkoxylated surfactant, the index m represents the average degree of alkoxylation in the mixture of surfactants. As such, the index m is at least about 0.01, preferably in the range from about 0.1 to about 30, more preferably from about 0.5 to about 10, most preferably from about 1 to about 5. Considering a heavy chain branched surfactant system comprising only alkoxylated surfactants, the value of the index m represents a distribution of the average degree of alkoxylation corresponding to m, which is precisely the number of units of alkoxylation (e.g., ethoxylation and / or Or propoxylation) may be a single specific chain corresponding to m.

Preferred heavy chain side chain surfactants of the invention suitable for use in the surfactant systems of the invention include Or chemical formula Surfactants, wherein a, b, d and e are integers such that a + b is 10-16 and d + e is 8-14; M is sodium, potassium, magnesium, ammonium and substituted ammonium, and these Is selected from a mixture of).

Surfactant systems of the invention comprising heavy chain side chain surfactants are preferably formulated in two embodiments. The first preferred embodiment comprises a heavy chain side chain surfactant formed from a raw material comprising up to 25% heavy chain side chain alkyl units. Thus, prior to mixing with other conventional surfactants, the heavy chain side chain surfactant component comprises up to 25% of the surfactant molecule, which is a non-linear surfactant.

A second preferred embodiment comprises a heavy chain side chain surfactant formed from a feed comprising about 25 to 70% heavy chain side chain alkyl units. Thus, prior to mixing with other conventional surfactants, the heavy chain side chain surfactant component contains about 25 to about 70% of the surfactant molecule, which is a non-linear surfactant.

The surfactant system of the laundry detergent composition of the present invention also contains one or more (preferably a mixture of two or more) heavy chain branched alkyl arylsulfonate surfactants, preferably surfactants in which the aryl unit is a benzene ring of the formula About 0.001%, preferably about 1%, more preferably about 5%, most preferably about 10% to about 100%, preferably 60%, more preferably 30% May contain%.

In the above formula,

L is an acyclic hydrocarbyl residue having 6 to 18 carbon atoms;

R ¹ , R ² and R ³ are each independently hydrogen or C ₁ -C ₃ alkyl, provided that R ¹ and R ² are not attached to the ends of the L unit;

M is a water soluble cation in which a and b together have a charge q satisfying charge neutrality.

Builder

The composition of the present invention preferably comprises at least one detergent builder or builder system, in particular when it comprises a surfactant. When present, the composition typically comprises from about 1 to about 80 weight percent, preferably from about 5 to about 50 weight percent, more preferably from about 10 to about 30 weight percent detergent builder.

The concentration of builders can vary widely depending on the end use application of the composition and its preferred physical form. If present, the composition typically comprises at least about 1% builder. Formulations typically comprise about 5 to about 50 weight percent, more preferably about 5 to about 30 weight percent detergent builders. The granule blend typically comprises about 10 to about 80 weight percent, more preferably about 15 to about 50 weight percent detergent builders. However, it does not exclude the lower or higher level of builders.

Inorganic or P-containing detergent builders include, but are not limited to, alkanolammonium salts of alkali metals, ammonium and polyphosphates, such as tripolyphosphate, pyrophosphate and glassy polymeric meta-phosphate, phosphonates, phytic acid, silicates , Carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates. However, non-phosphonate builders are needed in some locations. Importantly, the composition is surprisingly well even in the presence of so-called "weak" builders (compared to phosphates) such as citrate or even in the so-called "underbuilt" state, which can give rise to zeolite or layered silicate builders. Works.

An example of a silicate builder is the alkali metal silicate described in Rieck, US Pat. No. 4,664,839, issued May 12, 1987. NaSKS-6 is the trade name of the crystalline layered silicate sold by Hoechst (commonly abbreviated herein as "SKS-6").

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

Aluminosilicate builders are useful in the present invention. Examples of suitable aluminosilicate builders are described in US Pat. No. 4,274,975 to Corkhill et al., Which is incorporated herein by reference. Aluminosilicate builders are the most important for most currently marketed heavy liquid granule detergent compositions and may also be an important builder component in liquid detergent formulations. Aluminosilicate builder empirical formula _{[M z (zAlO 2) y} ] · xH and builder (wherein, z and y is an integer equal to or greater than 6 with ₂ O, molar ratio of z and y is in the range of 1.0 to about 0.5, x Is an integer from about 15 to about 264). Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are commercially available under the names Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X.

Organic detergent builders suitable for the purposes of the present invention include, but are not limited to, various kinds of polycarbonate compounds. As used herein, "polycarbonate" means a compound having a plurality of carboxylate groups, preferably three or more carboxylates. Polycarboxylate builders can generally be added to the composition in acid form, but may also be added in neutralized salt form. When used in salt form, alkali metal or alkanolammonium salts such as sodium, potassium and lithium are preferred.

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

Citrate builders such as citric acid and soluble salts thereof (particularly sodium salts) are polycarboxylate builders of particular interest for heavy liquid detergent formulations due to their availability from renewable sources and their biodegradability. Citrate can also be used in granular compositions, in particular in combination with zeolites and / or layered silicate builders. Oxydisuccinates are also particularly useful in the compositions and combinations described above.

Dispersant

A description of other suitable polyalkyleneimine dispersants that may optionally be combined with the bleaching stable dispersants of the present invention is described in US Pat. No. 4,597,898 to Van der Meer, issued July 1, 1986, incorporated herein by reference. number; European Patent Application No. 111,965 to Oh and Gosslink, published June 27, 1984; European Patent Application No. 111,984 to Gocelin, published June 27, 1984; European Patent Application No. 112,592 to Gocelin, published July 4, 1984; US Pat. No. 4,548,744 to Conner, issued October 22, 1985, and US Pat. No. 5,565,145 to Watson et al., Issued October 15, 1996. However, suitable clay / dirt dispersants or anti-deposition agents may be used in the laundry compositions of the present invention.

Also suitable are polymeric dispersants including polymeric polycarboxylates and polyethylene glycols for use in the present invention. Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconic acid, mesaconic acid, citraconic acid and methylenemalonic acid. . The presence of polymeric polycarboxylates or monomeric fragments herein that do not contain carboxylate radicals such as vinylmethyl ether, styrene, ethylene, and the like is suitable as long as the aforementioned fragments do not constitute at least about 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers useful herein are water-soluble salts of polymerized acrylic acid. The average molecular weight of said polymers in acid form is preferably about 2,000 to 10,000, more preferably about 4,000 to 7,000, most preferably about 4,000 to 5,000. Water soluble salts of such acrylic acid polymers may include, for example, alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. The use of this type of polyacrylate in detergent compositions is described, for example, in US Pat. No. 3,308,067 to Dill, issued March 7, 1967.

Acrylic / maleic acid based copolymers can also be used as preferred components of the dispersant / antideposition agent. Such materials include water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in acid form is preferably about 2,000 to 100,000, preferably about 5,000 to 75,000, more preferably about 7,000 to 65,000. The ratio of acrylate to maleate fragments in such copolymers is generally from about 30: 1 to about 1: 1, more preferably from about 10: 1 to 2: 1. The water soluble salts of the acrylic acid / maleic acid copolymers described above may include, for example, alkali metal, ammonium and substituted ammonium salts. Soluble acrylate / maleate copolymers of this type are also available on September 3, 1986, as well as European Patent Application No. 66915, published December 15, 1982, which describes the polymer comprising hydroxypropyl acrylate. Known material described in European Patent Application No. 193,360. Other useful dispersants also include maleic / acrylic acid / vinyl alcohol terpolymers. Such materials, including for example 45/45/10 terpolymers of acrylic acid / maleic acid / vinyl alcohol, are also described in EP 193,360.

Another polymeric material that may be included is polyethylene glycol (PEG). PEG not only exhibits dispersant performance but can also act as a clay dirt removal-re-deposition inhibitor. Typical molecular weight ranges for this purpose are 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.

Polyaspartates and polyglutamate dispersants may also be used, in particular with zeolite builders. The (average) molecular weight of the dispersant, such as polyaspartate, is preferably about 10,000.

Dirt release agent

The composition according to the invention may optionally comprise one or more dirt release agents. When used, dirt release agents generally comprise from about 0.01% to about 10%, preferably from about 0.1% to about 5%, more preferably from about 0.2% to about 3% by weight of the composition. The polymeric soil release agent is a hydrophilic fragment that hydrophilizes the surface of hydrophobic fibers such as polyester and nylon, and a hydrophobic that acts as an anchor for the hydrophilic fragments by being attached on the hydrophobic fibers and remaining attached above during the wash cycle is complete. It is characterized by having a fragment. This may allow stains that occur after treatment with a dirt release agent to be more easily cleaned in subsequent cleaning processes.

The following documents, all of which are incorporated herein by reference, describe suitable soil release polymers for use in the present invention: US Pat. No. 5,728,671 to Rohrbough et al., Issued March 17, 1998; U.S. Patent No. 5,691,298 to Gosselink et al., Issued November 25, 1997; US Pat. No. 5,599,782 to Pan et al., Issued February 4, 1997; US Patent No. 5,415,807 to Gosselink et al., Issued May 16, 1995; US Patent No. 5,182,043 to Morall et al., Issued January 26, 1993; US Patent No. 4,956,447 to Gosselink et al., Issued September 11, 1990; United States Patent No. 4,976,879 to Maldonado et al., Issued December 11, 1990; US Patent No. 4,968,451 to Scheibel et al., Issued November 6, 1990; US Pat. No. 4,925,577 to Borcher, Sr. et al., Issued May 15, 1990; US Patent No. 4,861,512 to Gosselink, issued August 29, 1989; US Patent No. 4,877,896 to Maldonado et al., Issued October 31, 1989; US Patent No. 4,771,730 to Gosselink et al., Issued October 27, 1987; US Patent No. 711,730 to Gosselink et al., Issued December 8, 1987; US Patent No. 4,721,580 to Gosselink, issued January 26, 1988; US Patent No. 4,000,093 to Nicole et al., Issued December 28, 1976; United States Patent No. 3,959,230 to Hayes, issued May 25, 1976; US Pat. No. 3,893,929 to Basadur, issued July 8, 1975, and European Patent Application 0 219 048 to Kud et al., Published April 22, 1987.

In addition, suitable soil release agents are all described in US Pat. No. 4,201,824 to Voileland et al., Incorporated herein by reference; US Pat. No. 4,240,918 to Lagasse et al .; US Patent No. 4,525,524 to Tung et al .; US Pat. No. 4,579,681 to Ruppert et al .; US Patent No. 4,220,918; U.S. Patent 4,787,989; European Patent No. 279,134 A to Rhone-Poulenc Chemie; European Patent No. 457,205 A (1991) to BASF and Unilerper En in 1974. It is described in German Patent No. 2,355,044 to Unilever N. V.

enzyme

Detergent and cleaning compositions of the present invention may also optionally contain one or more detergent enzymes. Such enzymes may include other proteases, amylases, cellulases and lipases. Such materials are known in the art and are commercially available under the trade names mentioned above. They may be incorporated into the non-aqueous liquid detergent compositions of the present invention in the form of suspensions, “marumes” or “prills”. Another suitable form of enzyme is in the form of a slurry of enzyme in a nonionic surfactant, for example the enzyme sold under the trade name "SL" by Novo Nordisk or under the trade name "LDP" by Novo Nordisk. Microencapsulation enzymes. Suitable enzymes and levels of use are described in US Pat. Nos. 5,576,282, 5,705,464, and 5,710,115.

Enzymes are added in the form of enzymes customary in the compositions of the present invention, and prills are particularly preferred for use herein. The size of such prills is generally in the range of about 100 to 1,000 microns, more preferably about 200 to 800 microns, and is suspended throughout the non-aqueous liquid phase of the composition. The prills in the compositions of the present invention have been found to exhibit particularly desirable enzyme stability with respect to retention of enzyme activity over time, relative to other enzyme forms. Thus, compositions using enzyme prills do not need to contain conventional enzyme stabilizers such as those commonly used when enzymes are introduced into aqueous liquid detergents.

However, the enzymes added to the compositions of the present invention may be in the form of granulates, preferably T-granulates.

“Detergent enzyme”, as used herein, means an enzyme that has a cleaning effect, stain removal effect, or other beneficial effect on a laundry, hard surface cleaning or face wash detergent composition. Preferred detergent enzymes include hydrolases such as proteases, amylases and lipases. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases and peroxidases. Highly preferred enzymes for automatic dishwashing are amylases and / or proteases, both of which are more suitable for bleaching despite successive advances, but are currently commercially available and improved forms with bleaching inactivity sensitivity remaining.

Examples of suitable enzymes include hemicellulose, peroxidase, protease, cellulase, xylanase, lipase, phospholipase, esterase, cutinase, pectinase, keratanase, reductase, oxidase, Phenol oxidase, lipoxygenase, ligninase, pullulanase, tanase, pentosanase, malanase, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase and Known amylases, or mixtures thereof, are included, but are not limited to these.

Examples of such suitable enzymes are described in US Pat. Nos. 5,705,464, 5,710,115, 5,576,282, 5,728,671 and 5,707,950.

Cellulase useful in the present invention includes both bacterial or fungicidal cellases. Preferably, they have an optimal pH of 5 to 12 and a specific activity of at least 50 CEVU / mg (cellulose viscosity units). Suitable cellulases are described in US Pat. No. 4,435,307, which describes fungicidal cellulases made from Humicolar insolens, Trichoderma, Thielavia and Sporotrichum, respectively. Japanese Patent No. 61078384 and WO 96/02653. EP 739 982 describes cellulase isolated from a novel Bacillus species. Suitable cellulase are also described in British Patent 2,075,028; British Patent 2,095,275; German Patent No. 2,247,832 and WO 95/26398.

An example of such cellulase is a cellulase produced by a strain of Humicola insolens (Humicola greece strain thermoide), in particular Humicola strain DSM 1800. Other suitable cellulases are derived from Humicola insolens, ^~ 43kD endoglucana derived from cellulase with a molecular weight of about 50KDa, with an isoelectric point of 5.5 and containing 415 amino acids and from Humicola insolens DSM 1800 exhibiting cellulase activity. And a preferred endoglucanase component has the amino acid sequence described in WO 91/17243. EGIII cellulase from the trichoderma longibrachiatum described in WO 94/21801 to Genencor is also a suitable cellulase. Particularly suitable cellulases are those that have color protection advantages. Examples of such cellulases are described in European Patent Application No. 91202879.2 (Novo), filed November 6, 1991. Carezyme and Celluzyme (Novo Nordisk A / S) are particularly useful. See WO 91/17244 and WO 91/21801. Other suitable cellulases for fabric protection and / or detergency are described in WO 96/34092, WO 96/17994 and WO 95/24471.

Cellulase, if present, is typically introduced into the cleaning composition at a level of 0.0001 to 2% pure enzyme, based on the weight of the cleaning composition.

Other preferred enzymes that may be included in the cleaning compositions of the present invention include lipases. Lipase enzymes suitable for cleaning use include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as described in British Patent No. 1,372,034. Suitable lipases include those that show a positive immunological crosslinking reaction with the antibody of lipase, produced by the microorganism Pseudomonas fluorescent IAM 1057. Such lipases are sold under the tradename Lipase P "Amano" from Amano Pharmaceutical Co. Ltd. of Nagoya, Japan, and are hereafter referred to as "Amano P". Other suitable conventional lipases are amino-CES; Lipases from Chromobacter viscosum, for example, Chromobacter bisium variant lipolyticum NRRLB 3673 from Toyo Jozo Co. of Dagata, Japan; U.S. of America. Chromobacter biskosium lipase from US Biochemical Corp. and Deisoynth Co., The Netherlands; And lipases from Pseudomonas gladioli. Especially suitable lipases composition and when used in the combined state is found to be very effective M1 Lipase ^R and lipoic Max (Lipomax ^R) according to the invention (Geest-bromo CAD's (Gist-Brocades)) and Li-polar agent ^R and re-polar Is a lipase like Ultra ^R (Novo). European patents 258 068, WO 92/05249 and WO 95/22615 to Novo Nordisk and WO 94/03578, WO 95/35381 and WO 96/00292 to Unilever The lipolytic enzymes described in the heading are also suitable.

Also suitable are kinases [EC 3.1.1.50], which can be considered as lipases of a certain kind, ie lipases that do not require interfacial activation. Addition of cutinase to the cleaning composition is described, for example, in WO-A-88 / 09367 (Genencor); WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilerfer).

Lipase and / or cutinase, if present, are typically introduced into the cleaning composition at levels of 0.0001 to 2% pure enzyme, based on the weight of the cleaning composition.

In addition to the lipases referenced above, phospholipases may be incorporated into the cleaning compositions of the present invention. Non-limiting examples of suitable phospholipases include EC 3.1.1.32 phospholipase A1; EC 3.1.1.4 phospholipase A2; EC 3.1.1.5 lysopolipase; EC 3.1.4.3 phospholipase C; EC 3.1.4.4. Phospholipase D is included. Commercially available phospholipases include Novo Nordisk A / S, Lexicase (LACITASE ^R ) and Sigma, phospholipase A2. If phospholipase is included in the composition of the present invention, it is preferred that amylase is also included. Without wishing to be bound by particular theory, the combining action of phospholipase and amylase is considered to provide substantial stain removal, in particular for fat / oil, starch and very colored stains and dirt. Preferably, the phospholipase and amylase, if present, are introduced into the composition of the invention in a pure enzyme weight ratio of 4500: 1 to 1: 5, preferably 50: 1 to 1: 1.

Suitable proteases are non. B. subtilis and b. Subtilisin (subtilisin BPN and BPN ') obtained from certain strains of B. licheniformis. Other suitable proteases have maximal activity over pH 8-12, developed by Novo Industries A / S of Denmark (hereinafter referred to as "Novo") and marketed as ESPERASE ^R. It is obtained from the strain of Bacillus. Methods of making such and similar enzymes are described in Novo's British Patent 1,243,784. Proteolytic enzymes are described in European Patent Application No. 87 303761.8, filed April 28, 1987, referred to herein as "Protease B", and in Europe of Venegas published October 29, 1986. Also included are modified bacterial serine proteases such as those described in patent application 199,404 and meaning modified bacterial serine proteolytic enzymes referred to herein as “protease A”. A variant of alkaline serine protease from Bacillus wherein lysine substitutes arginine at position 27, tyrosine substitutes valine at position 104, serine substitutes asparagine at position 123, and alanine substitutes threonine at position 274 Proteases, referred to herein as "protease C", are suitable. Protease C is described in EP 9915958: 4, corresponding to WO 91/06637 published May 16, 1991. In particular, genetically modified variants of protease C are also included herein.

Preferred proteases called “protease D” are the carbonyl hydrolases described in US Pat. No. 5,677,272 and WO 95/10591. The numbered positions are naturally occurring subtilisin or Bacillus lentus subtilisin from Bacillus amyloliquefaciens (co-pending U.S. Patent Application No. 60 / filed June 4, 1997). Other carbonyl hydrolases or subtilisin, such as 048,550 and PCT International Patent Application No. PCT / IB98 / 00853), in combination with one or more of the following residues corresponding to the equivalent amino acid residues corresponding to position 210: Also suitable are carbonyl hydrolase variants of the protease described in WO 95/10591, having an amino acid sequence derived by replacing a plurality of amino acid residues substituted in a precursor enzyme: +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.

Proteases described in EP 251 446 and WO 91/06637, proteases BLAP ^R described in WO 91/02792 and variants thereof described in WO 95/23221 are also suitable for the present invention.

See also high pH protease from Bacillus sp. NCIMB 40338 described in Novo WO 93/18140. Enzyme detergents comprising proteases, one or more enzymes and reversible protease inhibitors are described in Novo WO 92/03529 A. If desired, proteases with reduced adsorptivity and increased hydrolyzability can be used as described in WO 95/07791 to Procter & Gamble. Recombinant trypsin-type proteases suitable for detergents herein are described in WO 94/25583 to Novo. Other suitable proteases are described in European Patent No. 516 200 to Unilerfer.

Particularly useful proteases are described in PCT Publication WO 95/30010; WO 95/30011 and WO 95/29979. Suitable proteases are Esper cyclase, available from Novo Nordisk A O / S company of Denmark ^R, Alcalá the (ALKALASE ^R), Dura atom (DURAZYM ^R), Sabina the (SAVINASE ^R), Eberhard cyclase (EVERLASE ^R) and Khanna the ( KANNASE ^R) and jenen Accor International (formerly the Dutch Geest - Val Kane death) barracks hydratase (MASATASE ^R commercially available from captivity), barracks, Carl (MAXACAL ^R), Pro flops cyclase (PROPERASE ^R) and the barracks Pemba (MAXAPEM ^R It is marketed as).

Such proteolytic enzymes, if present, are introduced into the cleaning composition of the present invention at a level of 0.0001 to 2%, preferably 0.001 to 0.2%, more preferably 0.005 to 0.1% of the pure enzyme, based on the weight of the composition. .

Amylases (α and / or β) may be included for the removal of carbohydrate stains. WO 94/02597 describes cleaning compositions that incorporate mutant amylases. See also WO 95/10603. Other known amylases for use in the cleaning compositions include both α-amylases and β-amylases. α-amylases are known in the art and are described in US Pat. No. 5,003,257, EP 252,666, WO 91/00353; French Patent No. 2,676,456, European Patent No. 285,123, European Patent No. 525,610, European Patent No. 368,341 and British Patent Specification No. 1,296,839 (Novo). Other suitable amylases are in addition to the intermediates marketed from the increased stability of the enzymes described in WO 94/18314 and WO 96/05295 of Genencor, and Novo Nordisk A / S company described in WO 95/10603. Amylase variants with modification. Also suitable are the amylases described in EP 277 216.

Examples of common α-amylases include Purafect Ox Am ^R from Genencor, and Teramyl ^R , Ban ^R , and Fungamyl ^R available from Novo Nordisk A / S, Denmark. ) And Duramyl ^R ). WO 95/26397 describes other suitable amylases, wherein α-amylase is measured by Phadebas ^R α-amylase activity assays at temperatures ranging from 25 to 55 ° C. and pH values ranging from 8 to 10. Characterized by having a specific activity of at least 25% higher than the specific activity of mamil ^R. Variants of this enzyme described in WO 96/23873 (Novo Nordisk) are suitable. Other starch hydrolases with improved activity levels and thermal stability and properties for combination of higher activity levels are described in WO 95/35382.

Such starch hydrolase, if present, is introduced into the cleaning composition of the present invention at a level of 0.0001 to 2%, preferably 0.00018 to 0.06%, more preferably 0.00024 to 0.048%, of pure enzyme, based on the weight of the composition. .

The enzymes described above can be of any suitable origin, such as plant, animal, bacterial, fungicidal and yeast origin. This origin may additionally be mesophilic or extremophilic (frozen, psychrotropic, thermophilic, oppressive, alkalescent, eosinophil, basophilic, etc.). Such enzymes can be used in purified or unpurified form. Today, it is usually practical to modify wild enzymes by protein / genetic engineering techniques to optimize their performance efficiency in laundry detergents and / or fabric protection compositions of the present invention. For example, variants may be designed such that the suitability of the enzyme to the commonly encountered components of the composition can be increased. Alternatively, the variant may be designed such that the optimum pH, bleaching and chelant stability, catalytic activity, etc. of the enzyme variant are tailored to the particular cleaning article.

In particular, in the case of bleaching stability, attention should be paid to the surface charge for oxidation sensitive amino acid and surfactant compatibility. The isoelectric point of the enzymes described above can be modified by substituting some charged amino acids, for example increasing the isoelectric point may help to improve compatibility with anionic surfactants. The stability of the enzyme can be further enhanced by creating additional salt bridges and enhancing calcium binding sites to increase the chelant stability.

Any detergent enzyme described above, when present, is typically introduced into the cleaning composition at a level of 0.0001 to 2% pure enzyme, based on the weight of the cleaning composition. Enzymes can be added as individual single components (prills containing one enzyme, granulated products, stabilized liquids, etc.) or as mixtures of two or more enzymes (eg co-granulates).

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

The range of enzymatic materials and means for introducing them into the synthetic detergent composition also includes McCenty et al., Filed at Genencor International, in WO9307263 and WO9307260, WO8908694, and January 5, 1971. . US Patent No. 3,553,139. Enzymes are further described in US Pat. Nos. 4,101,457 and 4,507,219. Enzyme materials useful for liquid detergent formulations and methods for introducing them into such formulations are described in US Pat. No. 4,261,868.

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

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

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

(i) more than 25% specific activity of 25 to 55 ℃ range of temperature and pH value of from 8 to 10 range pade bath (Phadebas ^R) α- amylase the emitter mamil measured by activity assay of ^R a higher specific activity Characterized by having α-amylase; And / or

(ii) an α-amylase according to (i) comprising the amino acid sequence set forth in SEQ ID No. 1 or an α-amylase that is at least 80% identical to the amino acid sequence set forth in SEQ ID No. 1; And / or

(iii) an α-amylase according to (i) comprising the amino acid sequence set forth in SEQ ID No. 2 or an α-amylase that is at least 80% identical to the amino acid sequence set forth in SEQ ID No. 2; And / or

(iv) amino acid sequence N-terminus, His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn- Α-amylase according to (i) comprising Asp (SEQ ID No. 3) or α-amylase at least 80% identical to the amino acid sequence set forth in (SEQ ID No. 3) at the N-terminus; And / or

(v) α-amylases according to (i) to (iv), which can be obtained from a pro-alkaline Bacillus species; And / or

(vi) α-amylase according to (v), wherein the amylase can be obtained from any of strains NCIB 12289, NCIB 12512, NCIB 12513, and DSM 935; And / or

(vii) SEQ ID No. 1, ID No. 2 or ID No., respectively. Α-amylases, which exhibit positive immunological crosslinking reactivity with antibodies occurring against α-amylases having an amino acid sequence corresponding to 3; And / or

(viii) (1) SEQ ID No. 1, ID No. 2 or ID No., respectively. With an antibody having one of the amino acid sequences set forth in 4, or (2) at least 80% identical to at least one of the amino acid sequences described above and / or having an anti-amylase having one of the above amino acid sequences A variant of the parent α-amylase that is encoded by a DNA sequence that exhibits distant mechanical crosslinking reactivity and / or that is hybridized using the same probe as a DNA sequence encoding α-amylase having one of the amino acid sequences described above, wherein the variant is ( A) one or more amino acid residues of the parent α-amylase are deleted and / or (B) one or more amino acid residues of the parent α-amylase are replaced with different amino acid residues, and / or (C) one or more amino acid residues are replaced by the parent α-amylase. Inserted in proportion to amylase; has α-amylase activity and exhibits one or more of the following properties compared to the parent α-amylase: increased thermal stability; Increased oxidative stability; Reduced Ca ion dependence; Increased stability and / or α-starch hydrolysis activity at neutral to relatively high pH values; And increase or decrease the pi so that the isoelectric point (pI) value of the α-amylase variant is better matched to the pH of the medium.

A comparison of each amino acid sequence can be found in Lipman and Pearson in Science 227,1985, p. 1435, when executed via an algorithm such as that described, indicates that the polypeptide considered to be X% identical to the parent amylase is X% identical.

In the context of the present invention, the term “obtainable from” refers not only to amylases produced from Bacillus strains, but also to amylases produced in host organisms encoded by DNA sequences isolated from such Bacillus strains and transformed with DNA sequences. It is.

Enzyme stabilizers

Enzymes for use in detergents can be stabilized by a variety of techniques. Enzyme stabilization techniques are described and illustrated in US Pat. No. 3,600,319, EP 199,405 and EP 200,586. Enzyme stabilization systems are also described, for example, in US Pat. No. 3,519,570. Useful Bacillus sp. AC13 to produce proteases, xylanases and cellulases are described in WO9401532. As used herein, enzymes may be stabilized in the final composition in the presence of a water soluble source of such ions capable of supplying calcium and / or magnesium ions to the enzyme. Suitable enzyme stabilizers and levels of use are described in US Pat. Nos. 5,705,464, 5,710,115 and 5,576,282.

The following is a non-limiting example of a process for the preparation of bleach catalysts that effectively bleach stains in the absence of peroxygen sources.

Example 1

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

In a 250 ml three-necked round bottom flask equipped with thermometer, nitrogen inlet and magnetic stirrer, N, N'-bis (2-aminoethyl) -1,3-propanediamine (5.00 g, 31.3 mmol) and anhydrous ethanol (100 ml) Add. 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. Once the addition is complete, the solution is concentrated under reduced pressure to give a clear colorless oil. Isolated oil corresponds to formula (1) and yield is 100% (6.0 g).

The cyclic amine of formula 1 (6.0 g) is suspended in acetonitrile (100 ml). Potassium carbonate (25 g) and 1,3-propanediol ditosylate (12.61 g, 32.8 mmol) are added. The solution is stirred vigorously overnight at room temperature. The reaction is then warmed to 70 ° C., heat filtered using glass fiber filter paper and vacuum filtered. The resulting solid is washed with acetonitrile (100 ml). The acetonitrile filtrate is concentrated under reduced pressure to give the pale green oil of formula 2 in 100% yield (7.0 g).

Tetraamine (7.0 g) is dissolved in acetonitrile (150 ml). Methyl sulfate (2.5 equiv) is added and the reaction is warmed to 65 ° C. and stirred for 9 days. The solvent is removed under reduced pressure to give a brown oil of formula 3 in about 85% yield.

Distilled water (25 ml) and potassium carbonate (13.8 g) are added to a 250 ml round bottom flask. Anhydrous ethanol (75 ml) is added, the resulting biphasic solution is stirred and heated to 60 ° C. using an oil bath. Sodium borohydride (1.60 g, 42.3 mmol) and oil of formula 3 (10.0 g, 21.1 mmol) are added to the solution. The reaction is stirred at 60 ° C. for 75 minutes. The reaction mixture is placed in a separatory funnel and the ethanol layer is collected. The solvent is then removed under reduced pressure, and the resulting tan solid / oil is dissolved in 5N KCl (5 ml) and extracted with toluene (2 × 50 ml). Toluene was removed under reduced pressure, yielding 95% (5.2 g) of 5,12-dimethyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane of formula 4 as an oil after distillation. Obtained as

Anhydrous acetonitrile (5 L) was added to a flame dried 12 L three-necked round bottom flask equipped with a heating mantle, a stir bar and an oven dried condenser to give a 5,12-dimethyl-1,5,8,12-tetraaza-ratio. Obtain cyclo [6.6.2] hexadecane (484 g, 1.9 mol). The milky suspension is placed under 10 mm vacuum until the suspension boils, then the reaction vessel is flushed with argon. This degassing operation is carried out seven times. After the degassing operation is completed, manganese (II) chloride (228 g, 1.81 mol) is added. After refluxing for 4 hours with vigorous stirring, the suspension is immediately filtered through glass filter paper. The solvent is removed from the filtrate at 45 ° C. under reduced pressure to give a solid. The solid is then suspended in 500 ml toluene and then the supernatant is poured off. This washing process is repeated until the supernatant is colorless (usually seven times with about 7 x 500 ml of toluene). Drying the solid of formula 1 was dried under vacuum to yield 575 g (84%) of 5,12-dimethyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane manganese (II) chloride. do. The solid material is further washed and then the resulting solids are treated in a similar manner to give a second crop of the product. The total yield is 636 g (93%).

The following is a non-limiting example of a heavy duty liquid (HDL) laundry detergent composition according to the present invention.

weight% ingredient 2 3 4 5 C ₁₄ -C ₁₅ Alkyl E1.0 Sulfate 22.5 22.5 22.5 22.5 Linear alkyl benzene sulfonates 3.0 3.0 3.0 3.0 C ₁₀ amidopropyl DMA 1.5 1.5 1.5 1.5 C ₁₂ -C ₁₄ alkyl E7.0 3.0 3.0 3.0 3.0 Citric acid 2.5 2.5 2.5 2.5 C ₁₂ -C ₁₈ alkyl fatty acids 3.5 3.5 3.5 3.5 Rapeseed fatty acid 5.0 5.0 5.0 5.0 Protease 0.8 1.57 1.57 1.57 Amylase 0.055 0.088 0.088 0.088 Cellulase 0.188 0.055 0.055 0.055 Repolarase 0.06 - - - Meet 0.007 0.0033 0.0033 0.0033 Sodium metaborate 2.0 2.5 2.5 2.5 Ca formate / CaCl ₂ 0.02 0.10 0.10 0.10 Bleaching Catalyst ¹ 0.035 0.034 0.034 0.034 Antioxidants ² 0.23 0.25 0.25 0.25 Reducing agent ³ 0.02 - - - Reducing agent ⁴ - - 0.0042 0.0083 Hydrophobic Dispersants ⁵ 0.65 0.76 0.76 0.76 Soil Release Agent ⁶ 0.147 - - - Soil Release Agent ⁷ - 0.10 0.10 0.10 Foam inhibitor 0.60 0.60 0.60 0.60 Water and handful Residual amount Residual amount Residual amount Residual amount 5,12-dimethyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane manganese (II) chloride 2. Butylated hydroxy toluene 3. Potassium metabisulfite 4. Potassium sulfite 5. PEI 189 E15-186 according to Vander Mir US Patent 4,597,898, issued July 1, 1986. A releasing agent according to Gosselink, U.S. Patent No. 4,702,857, issued October 27, 1987 7. Spent release agent according to US Patent No. 4,968,451 to Shaibel et al. Issued November 6, 1990.

weight% ingredient 6 7 8 9 C ₁₄ -C ₁₅ Alkyl E1.0 Sulfate 22.5 22.5 - - C ₁₂ -C ₁₅ Alkyl E1.8 Sulfate 23.5 23.5 Linear alkyl benzene sulfonates 3.0 3.0 3.0 3.0 C ₁₀ amidopropyl DMA 1.5 1.5 - - C ₁₂ -C ₁₄ alkyl E7.0 3.0 3.0 2.0 2.0 Citric acid 2.5 2.5 2.5 2.5 Sodium sulfate - - 1.75 1.75 C ₁₂ -C ₁₈ alkyl fatty acids 3.5 3.5 5.0 5.0 Rapeseed fatty acid 5.0 5.0 6.5 6.5 Protease 1.57 1.57 1.57 1.57 Amylase 0.088 0.088 0.088 0.088 Cellulase 0.055 0.055 0.055 0.055 Meet 0.0033 0.0033 0.0033 0.0033 Sodium metaborate 2.5 2.5 2.5 2.5 Ca formate / CaCl ₂ 0.10 0.10 0.10 0.10 Bleaching Catalyst ¹ 0.034 0.004 0.04 0.04 Antioxidants ² 0.25 0.025 0.25 0.25 Reducing agent ³ - - 0.01 - Reducing agent ⁴ 0.0083 0.001 - 0.01 Hydrophobic Dispersants ⁵ 0.76 0.76 1.20 1.20 Soil Release Agent ⁶ - - - - Soil Release Agent ⁷ 0.10 0.10 0.10 0.10 Foam inhibitor 0.60 0.60 0.60 0.60 Water and handful Residual amount Residual amount Residual amount Residual amount 5,12-dimethyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane manganese (II) chloride 2. Butylated hydroxy toluene 3. Potassium metabisulfite 4. Potassium sulfite 5. PEI 189 E15-186 according to Vander Mir US Patent 4,597,898, issued July 1, 1986. A releasing agent according to Gosselink, U.S. Patent No. 4,702,857, issued October 27, 1987 7. Spent release agent according to US Patent No. 4,968,451 to Shaibel et al. Issued November 6, 1990.

Claims (12)

(A) a catalytically effective amount of a transition metal bleach catalyst, which is a complex of a transition metal and a crosslinked bridged macropolycyclic ligand; (B) an effective amount of stabilizer selected from (i) at least one antioxidant, (ii) at least one reducing agent, and (iii) mixtures thereof; And (C) comprises a residual amount of carrier and other accessory ingredients, However, a bleaching composition for achieving a bleaching action without the need of adding an organic or peroxygen compound which is substantially free of an organic or inorganic peroxygen compound. The method of claim 1 wherein the transition metal bleach catalyst is (i) 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), Ru (IV) and transition metals selected from the group consisting of (ii) (a) at least four donor atoms separated from each other by covalent bonding of two or three non-donor atoms, two to five of which donor atoms being coordinated to the same transition metal atom in the complex Organic macrocycle ring containing; (b) a crosslinked bridge of 2 to 10 atoms covalently linking two or more non-contiguous donor atoms of the organic macrocycle ring, wherein the covalently bonded non-contiguous donor atoms are coordinated to the same transition metal in the complex Bridgehead donor atoms; (c) optionally a crosslinked bridged macrocyclic ligand comprising at least one non-macropolycyclic ligand and coordinating to the same transition metal by 4 to 5 donor atoms. The composition of claim 1 or 2, wherein the organic macrocycle ring comprises at least four donor atoms of N separated from each other by covalent bonds of two to four non-donor atoms and coordinated to the same transition metal atom. . The composition of claim 1 comprising at least 1 ppb of a transition metal bleach catalyst. The composition of claim 1 wherein the transition metal bleaching catalyst is 5,12-dimethyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane manganese (II) chloride. The method of claim 1 wherein the stabilizer is a mixture of 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 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-dihydro-benzofuran, 5-benzyloxy-3-hydroxymethyl-2,2,4,6,7-pentamethyl-2,3-dihydro-1- Antioxidant selected from the group consisting of benzofuran, 3-hydroxymethyl-5-methoxy-2,2,4,6,7-pentamethyl-2,3-dihydro-1-benzofuran and mixtures thereof Phosphorus composition. The composition of claim 1 wherein the stabilizer is a reducing agent selected from the group consisting of sodium sulfite, potassium sulfite and mixtures thereof. (a) a catalytically effective amount of a transition metal bleach catalyst that is a complex of a transition metal and a crosslinked bridged macropolycyclic ligand; an effective amount of stabilizer selected from (b) (i) at least one antioxidant, (ii) at least one reducing agent, and (iii) mixtures thereof; And (c) comprises a residual amount of carrier and other accessory ingredients, However, the composition for liquid washing, laundry preimpregnation or pretreatment substantially free of an organic or inorganic peroxygen compound. The method of claim 8 wherein the catalyst is (i) 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) transition metals selected from the group consisting of (ii) (a) crosslinked bridged macropolycyclic ligands of formula (I) having four or five denticities; (b) crosslinked bridged macropolycyclic ligands of formula (II) having 5 or 6 protrusions; (c) crosslinked bridged macropolycyclic ligands of formula III having 6 or 7 protuberances, and (d) a composition comprising a crosslinked bridged macropolycyclic ligand, optionally selected from the group consisting of one or more non-macropolycyclic ligands. Formula I Formula II Formula III In Chemical Formulas I to III, Each E unit is a residue of formula (CR _n ) _a -X- (CR _n ) _{a '} wherein X is selected from the group consisting of oxygen, sulfur, -NR- and phosphorus, or E is selected from formula (CR _n ) _a -(CR _n ) is a covalent bond to represent a residue of _{a '} ), and the sum of a + a' in each E unit is independently selected from 1 to 5, Each G unit is a residue (CR _n ) _b , Each R unit is independently selected from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl and heteroaryl, or two or more R units are covalently bonded to form an aromatic, heteroaromatic, cycloalkyl or heterocycloalkyl ring , The D unit is a donor atom each independently selected from the group consisting of nitrogen, oxygen, sulfur and phosphorus, at least two atoms comprising the D unit are bridgehead donor atoms coordinated to a transition metal, The B unit is a carbon atom, a D unit, or a cycloalkyl or heterocyclic ring, n is an integer independently selected from 1 and 2, each of which meets the valence of the carbon atom to which the R unit is covalently bonded, n 'is an integer independently selected from 0 and 1, each of which meets the valence of the D donor atom to which the R residue is covalently bonded, n ″ is an integer independently selected from 0, 1 and 2, each of which meets the valence of the B atom to which the R residue is covalently bonded, a and a 'are each independently an integer selected from 0 to 5, wherein the sum of all a + a' values in the ligand of formula I is in the range of 8 to 12, and all a + a 'values in the ligand of formula II The sum of is in the range of 10 to 15, and the sum of all a + a 'values in the ligand of formula III is in the range of 12 to 18), b is an integer each independently selected from 0 to 9, or in the formula, at least one covalently linking D and B atoms, as long as at least two (CR _n ) _b covalently bonds two D donor atoms to the B atom; (CR _n ) _b residues are absent and the sum of all indexes b is in the range of 2-5. The method of claim 9, wherein the catalyst is 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-, Groups consisting of organic phosphates, organic phosphonates, organic sulfates, organic sulfonates, and aromatic N donors including pyridine, pyrazine, pyrazole, imidazole, benzimidazole, pyrimidine, triazole and thiazole , R is H, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl) A composition comprising a non-macropolycyclic ligand. The fabric that needs to be cleaned, (a) a catalytically effective amount of a transition metal bleach catalyst that is a complex of a transition metal and a crosslinked bridged macropolycyclic ligand; an effective amount of stabilizer selected from the group consisting of (b) (i) at least one antioxidant, (ii) at least one reducing agent, and (iii) mixtures thereof, and (c) comprises a residual amount of carrier and other accessory ingredients, Provided that the fabric is contacted with an aqueous or non-aqueous solution containing a composition comprising less than 0.1% of organic or inorganic peroxygen compounds, wherein the concentration of the transition metal bleaching catalyst in the aqueous solution is at least 0.01 ppb. How to bleach stains and stains. The non-macropolycyclic ligand of claim 2, wherein the non-macropolycyclic ligand is 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 groups consisting of aromatic N donors including pyridine, pyrazine, pyrazole, imidazole, benzimidazole, pyrimidine, triazole and thiazole, wherein R is H, substituted or unsubstituted Unsubstituted alkyl, or substituted or unsubstituted aryl).