CZ306399A3 - Bleaching preparations containing metal bleaching catalyst and bleaching activators and/or organic percarboxylic acids - Google Patents

Abstract

New detergents or cleaners include an effective amount bleach activator and / or organic peroxyacid, catalytically an effective amount of a transition bleach catalyst metal and other additive material which is usually oxygenated bleaching agent.

Description

Technical field

The invention relates to detergent and detergent additive formulations and methods of using them. The formulations include selected transition metals such as Mn, Fe or Cr with selected macropolycyclic ligands in combination with bleach activators and / or organic percarboxylic acids, preferably hydrophobic and / or hydrophilic bleach activators. More particularly, the present invention relates to the catalytic oxidation of dirt and stains using cleaning compositions comprising bleach activators and / or organic percarboxylic acids and said metal catalysts, wherein the stains and dirt are on the surface of fabrics, dishes, uppers, teeth and the like, as well. as it relates to preventing the transfer of colors when washing fabrics. The compositions include bleach activators and / or organic percarboxylic acids, detergent builders, and catalysts including complexes of manganese, iron, chromium, and other suitable transition metals with some cross-bridged macropolycyclic ligands. Preferred catalysts include transition metal complexes with ligands which are polyazamacropolycycles, especially including some azamacrobicyclics such as bridged cyclam derivatives.

BACKGROUND OF THE INVENTION

The destructive effect of manganese on fabrics during bleaching has been known since the 19th century. In the 1960s and 1970s, efforts were made to incorporate simple Mn (II) salts into detergents, but without visible commercial success. Presently, bleaching agents have been disclosed containing metal catalysts with macrocyclic ligands. Preferred catalysts include manganese catalysts of small macrocycles, in particular 1,4,7-trimethyl-1,4,7-triazacyclononane compounds. These catalysts are said to catalyze the process of bleaching various spots with peroxy compounds. Several are said to be effective in washing and bleaching substrates, including dishwashing and laundry washing applications, in the textile and paper industry, and in the manufacture of wood pulp. However, these metal-containing bleach catalysts, and especially manganese-containing catalysts, still have some disadvantages, such as tendency to destroy fabrics, relatively high cost, high coloration, and the ability to spot or discolour substrates locally.

The complex metal cation salts described in U.S. Patent 4,888,032 (Bush, Dec. 19, 1989) have been reported to reversibly complex oxygen and are believed to be useful for closing oxygen and separating it from air. A wide variety of ligands are believed to be useful, including macrocyclic ring structures and bridging groups. See. also D. H. Busch, Chemical Reviews, (1993), 93, 847-880, eg, discussion of superstructures of polydentate ligands on pages 856-857 and references cited therein; Coltrain et al., Oxygen Activation by Transition Metal Complexes of Macrobicyclic CyclideneLigands in The Activation of Dioxygen and Homogeneous Catalytic Oxidation, Ed. E. H. R. Barton, et al. (Plenum Press, NY, 1993), pp. 359-380.

Currently, technical literature on azamacrocycles is growing rapidly. Among others, Hancock et al., J. Chem. Soc., Chem. Commun. (1987), 1129-1130; Weisman et al., Synthesis and Transition Metal Complexes of New Cross-Bridged Tetraamine Ligands, Chem. Commun. (1996) 947-848; U.S. Patents 5,428,180, 5,504,075 and 5,126,464 all of Burrows et al .; U.S. Patent 5,480,990 (Kiefer et al.) And U.S. Patent 5,374,416 (Rousseaux et al.). None of these hundreds of references indicate which of the many novel ligands and / or complexes might be commercially useful in bleaching compositions. This history does not reveal the possibility that catalytic oxidation can change almost all classes of organic compounds to produce valuable products, but successful applications such as bleaching hard surfaces or bleaching fabrics depend on a number of complex conditions including the activity of the putative catalyst, its survival under reaction conditions, its selectivity and presence of unwanted side reactions or overreaction.

In view of the long-term needs, there is ongoing research into an excellent bleaching composition comprising a bleach catalyst based on a transition metal, but so far without commercial success at this point, particularly with laundry detergents with transition metal catalysts. Also due to the constant need for improved detergents of all kinds, which exhibit excellent bleaching and cleaning capabilities without having such disadvantages as destruction or discolouration of the cleaned material and due to the known technical limitations of existing transition metal catalysts for detergent applications, especially in aqueous solutions at high pH, it would be very useful to identify which of those thousands of potential transition metal complexes could be successfully involved in laundry and cleaning products. It is, therefore, an object of the present invention to provide excellent cleaning compositions containing selected bleach catalysts based on intermediate transitions.

metals with detergent or cleaning additives that would address one or more of the known limitations of such formulations.

Surprisingly, it has now been found that, for use in laundry and solid surface cleaning, transition metal catalysts having certain bridged macropolycyclic ligands in which the metal ions slowly dissociate only under conditions that would destroy complexes with normal complexes have exceptional kinetic stability, and which further have exceptional thermal stability. Furthermore, it has surprisingly been found that these catalysts, in combination with bleach activators and / or organic percarboxylic acids, preferably hydrophobic or hydrophilic bleach activators, provide additional bleaching and cleaning benefits and properties. Thus, the compositions of the present invention can provide one or more important properties. These include improved efficacy of the formulation and in some cases even a synergistic effect with one or more primary oxidants such as hydrogen peroxide or monoperoxosulfate; cleaning compositions comprising preferably Mn (II), in which the catalyst is particularly well colored in color with other detergent components, a catalyst having a weak to no color. The formulations provide great flexibility in formulation into consumer products where product aesthetics are very important and are very effective on many types of soils with dirty substrates, including a number of dirty and stained fabrics or rigid surfaces. The formulations allow compatible incorporation of many types of detergent additive with excellent results. In addition, the compositions reduce or even minimize the tendency to soiling or destroy these surfaces.

These and other points are provided in the present invention as will be demonstrated in the following description.

Laundry bleaching has been reviewed in Kirk Othme's Enycklopedia of Chemical Technology, 3rd Edition and 4th Edition under several headings such as Bleaching Agents, Detergents and Peroxy Compounds. The use of amide derivative bleach catalysts in laundry laundry detergents is described in U.S. Patent 4,634,551. The use of manganese with various ligands for enhancing bleaching is described in the following US Patents US 4,430,243, US 4,728,455, US 5,246,621, US 5,244,594, US 5,284,944, US 5,194,416, US 5,246,612, US 5,256,779, US 5,280,117, US 5,274,147, US 5,153,161 US 5,114,606; US 5,114,611. See. also EP 549,271, EP 544,490 A1, EP 549,272 A1 and EP 544,440 A2.

US 5,580,485 describes bleaching and oxidation catalysts comprising an iron complex having the formula A [LFeX _n ] ^of Y _q (A) or precursors thereof in which Fe is iron in oxidation states II;

III, IV or V, X represents a coordination particle such as H 2 O, ROH, NR 3, RCN, OH ', OOH', rs; ro ', rcoo; ocn; scn; n ₃ ; cn; F; cr, bf, r, o ₂ ; no ₃ ; no ₂ ', so ₄ ² ; so3 ² ; PO 4 ^3- or aromatic N donors such as pyridines, pyrazines, pyrazoles, imidazoles, benzimidazoles, pyrimidines, triazoles and thiazoles with R being H, optionally substituted alkyl, optionally substituted aryl; n is 0-3; Y is a counterion whose type depends on the charge of the complex; q = z / [charge Y]; z denotes the charge of the complex and is an integer that can be positive, zero or negative; when z is positive Y is an anion such as F, Cl, Br, Γ, NO3 ', BPk', C1O4 ', BF4, PF6, RSO3', RSO4 ', SO4 ² ', CF3SO ₃ ', RCOO and the like; when Z is negative Y is a cation such as an alkali metal, alkaline earth metal or (alkyl) ammonium cation and the like; L represents a ligand that is an organic molecule containing a plurality of heteroatoms, e.g., N, P, O, S, and the like, that coordinate (all or part of them) to a central iron atom. It is said that the most preferred ligand is N, N-bis (pyridin-2-ylmethyl) -bis (pyridin-2-yl) methylamine, N ₄ Py. Fe complex catalysts are said to be useful for a peroxy compound-based bleach system or precursor thereof, and are suitable for use in laundry washing and bleaching substrates including laundry washing, dish washing and hard surface cleaning. Alternatively, the complexes are suitable for use in the textile, paper and pulp industries.

The field of chemistry of transition metal macrocycles is enormously extensive. for example, Heterocyclic compounds: Aza-crown macrocycles, J. S. Bradshaw et al., Wiley-Interscience, (1993), which also describes a number of syntheses of these ligands. See. especially the table beginning on page 604. U.S. Pat. No. 4,888,032 describes complexes of cationic metal salts.

Cross-bridged, i.e., bridged by non-adjacent nitrogen, cycles (1,4,8,11-tetraazacyclotetradecane) are described in Weisman et al., J. Amer. Chem. Soc., (1990) 112 (23), 8604-8605. More specifically, Weisman et al., Chem. Commun., (1996), 947-948, discloses novel cross-bridged tetraamine ligands that are bicyclo [6.6.2], [6.5.2] and [5.5.2] systems and their complexation with Cu (II) and Ni ( II) and shows that ligands coordinate metals in the form of cavity. Specific complexes include ligands 1.1:

: n

1.1

Wherein A is hydrogen or benzyl and (a) m = n = 1 or (b) m = lan = 0 or (c) m = n = 0, including copper (II) chloride ligand complexes, wherein: A = H and m = n = 1; cupric perchlorate complex wherein A = H and m = n = 1 or m = n = 0; a nickel bromide-ligand complex wherein A = H and m = n = 1. In some cases, the halide in these complexes is a ligand, in some cases the halide is present as an anion. This range of complexes appears to be even larger than similar compounds where cross-bridging is not through neighboring nitrogen.

Ramasubbu and Wainwright, J. Chem. Soc., Chem. Commun., (1982), 277-278, on the other hand, describes a structurally cycled bridged by adjacent nitrogen donors. Ni (II) forms a light yellow mononuclear diperchlorate complex having one mole of ligand in a planar square configuration. Kojima et al., Chemistry Letters, (1996), pp. 153-154, discloses novel optically active dinucleic complexes of a structurally reinforced tricyclic macrocycle.

Bridging by alkylation of saturated polyazamacrocycles as a means to create structural rigidity is described in Wainwright, Inorg. Chem., (1980), 19 (5), 1396-8. Mali, Wade and Hancock disclose a cobalt complex of a structurally reinforced macrocycle. J. Chem. Soc., Dalton Trans., (1992), (1), 67-71. Seki et al. describes the synthesis and structure of chiral dinucleic Cu (II) complexes of a novel reinforced hexaazamacrocyclic ligand; viz. Mol. Cryst. Liq. Cryst. Sci. Technol., Sec. A (1996), 276, pp. 79-84; viz. also the corresponding works of the same authors in the same journal 276, pp. 85-90 and 278, pp. 235-240. [Μη (ΙΙΙ) 2 (μO) (m-O2CMe) 2L2] ²⁺ and [Mn (IV) 2 (mO) 3L2] ²⁺ complexes, derived from a series of N-substituted 1,4,7-triazacyclononanes, are described in Koek. et al. J. Chem. Soc., Dalton Trans., (1996), 353362. An important earlier work by Wieghardt and co-workers on transition metal complexes with 1,4,7-triazacyclononane, including manganese complexes, is described in Wieghardt et al., Angew. Chem. Dormitory. Ed. Engl. (1986), 25, 1030-1031 and Wieghardt et al., J. Amer. Chem. Soc., (1988), 110, 7398. Ciampolini et al., J. Chem. Soc., Dalton Trans. (1984), pp. 1357-1362, describes the synthesis and characterization of the macrocycle 1,7-dimethyl-1,4,7,10-tetraazacyclododecane and some of its Cu (II) and Ni (II) complexes. , including both planar square Ni complexes and cis-octahedral complexes with a macrocycle coordinated in a folded configuration at four locations around the central nickel atom. Hancock et al., Inorg. Chem., (1990), 29, 1968-1974, describes ligand design approaches for complexation in aqueous media, including the size of the chelate cycle as a basis for size-based control of selectivity to the metal ion. Thermodynamic data for macrocycle interactions with cations, anions, and neutral molecules are summarized in Izatt et al., Chem. Rev., (1995), 95, 2529-2586 (478 references). Bryan · · · · · · · · · · · · · ·

et al., Inorganic Chemistry, (1975), 14, No. 2, pp. 296-299, describes the synthesis and characterization of Mn (II) and Μη (ΙΠ) complexes with meso-5,5,7,12,12, 14-hexamethyl-1,4,8,1-tetraazacyclotetradecane ([14] aneN4). Isolated solids are often contaminated with a free ligand or excess metal salt, and attempts to prepare chloride and bromide derivatives have resulted in solids of variable composition that could not be purified by repeated crystallization. Costa and Delgado, Inorg. Chem., (1993), 32, 5257-5265, discloses metal complexes such as Co (II), Ni (II) and Cu (II) complexes with pyridine-containing macrocycles. Cross-bridged cyclene derivatives such as 4,10-dimethyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane salts are described in Bencini et al. Supramolecular Chemistry, 3, pp. 141-146. U.S. Patent 5,428,180 and similar work by Cynthia Burrows et al., U.S. Patent 5,272,056 and U.S. Patent 5,504,075, describe the pH dependence of oxidation using cyclame or its derivatives, oxidation of alkenes to epoxides using metal complexes of these derivatives, and pharmaceutical applications. Hancock et al., Inorganica Chimica Acta, (1989), 164, 73-84, describes under the title complexes of structurally reinforced macrocyclic ligands with a strong ligand field synthesis of low-spin Ni (II) complexes with three novel bicyclic macrocycles. The complexes appear to exhibit an almost coplanar arrangement of the four donor atoms and metals, regardless of the presence of the bicyclic ligand arrangement. Bencini et al., J. Chem. Soc., Chem. Commun., (1990), 174-175, describes the synthesis of a small azacrylate compound 4,10-dimethyl-1,4,7,10,15-pentabicyclo [5.5.5] heptadecane which complexes lithium in the cavity. Hancock and Martell, Chem. Rev., (1989), 89, 1875-1914, summarizes the design of a ligand for selectively complexing metal ions in aqueous solutions. Conformers of cyclamide complexes are discussed on page 1894, including a composite conformer - see p. Giant. 18 (cis-V). The article contains an index. In an article entitled Structurally Reinforced Macrocyclic Ligands Showing Very Increased Selectivity for Metal Ions by Matching Metal Ion Size and Macrocycle Cavity, Hancock et al., J. Chem. Soc., Chem. Commun., (1987), 11291130, describes stability constants for Cu (II), Ni (II) and other metal complexes of some bridged macrocycles having a structure similar to piperazine. Many other macrocycles are described in the literature including pendant groups and a wide variety of intracyclic and exocyclic substituents. In short, although the literature on transition metal complexes and macrocycles is enormous, few references have been made to cross-bridged tetraaza- and pentaazamacrocycles, and there is probably no one to discuss the use of transition metals alone or their complexes for use in bleaching. detergentech.

• · ·

SUMMARY OF THE INVENTION

The present invention relates to laundry and cleaning compositions comprising;

(a) an effective amount, preferably from 1 ppm to about 99.9%, more preferably from 0.1% to about 25%, of a bleach activator, preferably a bleach activator selected from the group of hydrophobic bleach activators, hydrophilic bleach activators and mixtures thereof;

(b) a catalytically effective amount, preferably from 1 ppm to 99.9%, more preferably from 0.001 ppm to 49%, preferably from 0.05 to about 500 ppm (wherein ppb denotes parts per billion and ppm denotes parts per million a transition metal bleach catalyst, wherein said transition metal bleach catalyst comprises a transition metal complex selected from the group consisting of Mn (II), Mn (III), Mn (IV), Mn (V), Fe (II) , Fe (III), Fe (IV), Co (II), Co (II), Co (III), Ni (I), Ni (II), Ni (III), Cu (I), Cu (II) , Cu (III), Cr (III), 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) coordinated with the macropolycyclic ligand, preferably a cross-bridged macropolycyclic ligand having at least 4 donor atoms, at least two of which are bridged donor atoms, and (c) an addition to 100% of one or more accessory materials, preferably comprising oxygen bleaching agent.

Preferred bleaching compositions include:

(a) an effective amount, preferably from about 1 ppm to about 99.9%, more preferably from about 0.1% to 25% of a bleach activator selected from the group consisting of a hydrophobic bleach activator such as N, N, N ', N tetraacetylethylenediamine and mixtures thereof;

(b) a catalytically effective amount, preferably from 1 ppb to about 99.0%, more preferably from 0.001 ppm to about 49%, preferably from 0.05 ppm to about 500 ppm of a transition metal catalyst, said catalyst comprising a complex transition metal and cross-bridged macropolycyclic ligand, where:

(1) said transition metal is selected from the group consisting of Mn (II), Mn (III), Mn (IV), Fe (II), Fe (III), Cr (II), Cr (III), Cr (IV) Cr (V) and Cr (VI);

(2) said cross-bridged macropolycyclic ligand is coordinated by four or five donor atoms to the same transition metal atom and comprises:

(i) an organic macrocyclic ring containing four or more donor atoms selected from the group consisting of N, optionally O or S, wherein at least two of these donor atoms are N (preferably at least 3, more preferably at least 4 of these atoms are N), wherein are separated from each other by the covalent linking of 2 or 3 non-donor atoms, two to five (preferably three to four, more preferably four) of these atoms are coordinated to one transition metal in the complex;

(ii) a cross-bridged chain that covalently connects at least two non-adjacent N donor atoms in an organic macrocyclic ring, wherein said covalently linked non-adjacent N donor atoms are bridged N donor atoms that are coordinated to one transition metal complex and wherein said cross-bridged chain comprising 2 to about 10 atoms (preferably, the bridging chain is selected from 2, 3 or 4 non-donor atoms and 4-6 non-donor atoms with another, preferably N, donor atom); and (iii) 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', N ₃ ', CN', F ', Cl, Br' , Γ, O ₂ ', NO ₃ ', NO ₂ ', SO4 ² ', SO ₃ ² ', PO4 ³ ', organic phosphates, 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 with alkyl, optionally substituted with aryl, and (c) an addition of up to 100%, preferably at least 0.1%, of one or more additional laundry or cleaning materials, preferably comprising an oxygen bleach.

The amount of transition metal base catalyst, bleach activator and / or organic percarboxylic acid and filler materials may vary depending on the particular application. For example, the compositions of the invention may be supplied as concentrates in which the catalyst and bleach activator and / or the percarboxylic organic acid may be present at high concentrations, eg 0.01% to 80% or more. The invention also encompasses compositions comprising catalysts and an activator with bleach and / or organic percarboxylic acid at their utility concentrations, such compositions including those where the catalyst is diluted, e.g., to ppb concentrations. Medium concentration formulations, eg, those containing from 0.01 ppm to about 500 ppm, more preferably from 0.05 ppm to about 50 ppm, even more preferably from 0.1 ppm to about 10 ppm transition metal catalyst; from 1 ppm to about 10,000 ppm, preferably from about 10 ppm to about 5000 ppm of bleach activator and / or organic percarboxylic acid (preferred concentrations for hydrophobic and hydrophilic bleach activators are from about 1 ppm to about 3000 ppm, more preferably from about 10 ppm ppm to about 1000 ppm) and the supplement. Up to 100%, preferably at least 0.1%, typically about 99% or more is in liquid or solid form (eg, fillers, solvents and additives adapted for a particular application).

The present invention also relates to laundry and cleaning compositions comprising:

(a) an effective amount, preferably from 1 ppm to about 99.9%, more preferably from 0.1% to about 25%, of a bleach activator and / or an organic percarboxylic acid;

(b) a catalytically effective amount, preferably from 1 ppb to about 99.9% of a transition metal bleach catalyst, a transition metal complex and a cross-bridged macropolycyclic ligand, and (c) an addition to 100% of one or more accessory materials, preferably comprising an oxygen bleach.

The present invention also relates to laundry and cleaning compositions comprising:

(a) an effective amount, preferably from 1 ppm to about 99.9%, more preferably from 0.1% to about 25%, of a bleach activator and / or an organic percarboxylic acid;

(b) a catalytically effective amount, preferably from 1 ppb to about 49% of a transition metal bleach catalyst and a macropolycyclic ligand, preferably a cross-bridged macropolycyclic ligand, wherein:

(1) said transition metal is 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 (II), Ni (II), Ni (III), Cu (I), Cu (II), Cu (III), Cr (II), Cr (III) , Cr (V), Cr (V), Cr (VI), V (ID), V (TV), V (V), Mo (IV), Mo (V), Mo (VI), W (IV) W (V), W (VI), Pd (II), Ru (II), Ru (ffl) and Ru (TV);

(2) said macropolycyclic rigid ligand is coordinated by at least four, preferably four or five donor atoms to the same transition metal and comprises:

(i) an organic macrocyclic ring containing four or more donor atoms (preferably at least 3, more preferably at least 4 of these atoms are N), separated from each other by a covalent linkage containing at least one, preferably 2 or 3 non-donor atoms, two to five (preferably three to four, more preferably four) of these donor atoms are coordinated in complex with the same transition metal;

(ii) a linker group, preferably a cross-bridging chain, covalently linking at least 2 (preferably non-adjacent) donor atoms of the organic macrocyclic ring, wherein the altered covalently joined (preferably non-adjacent) donor atoms are donor bridge atoms that are coordinated to the same intermediate and wherein said linking group (preferably a cross-bridging group) comprises from 2 to about 10 atoms (preferably, the cross-bridging group is selected from the group consisting of 2, 3 or 4 non-donor atoms and 4-6 non-donor atoms with another and (iii) optionally, one or more non-macropolycyclic ligands, preferably monodentate ligands such as those selected from the group consisting of H 2 O, ROH, nr ₃ , rcn, oh; ooh; rs; ro; rcoo; ocn; scn; n ₃ ; cn; F; cr, Br; r, o ₂ ; no ₃ ; no ₂ ', SO4 ² ; SO ₃ ² ', PO ^{4 3} ', organic phosphates, organic sulfates, organic sulfonates and aromatic N donors such as pyridines, pyrazines, pyrazoles, imidazoles, benzimidazoles, pyrimidines, triazoles and thiazoles wherein R is Η, optionally substituted with alkyl, optionally substituted with aryl (specific examples of monodentate ligands include phenolates, acetates and the like); and (c) at least 0.1%, preferably B%, of one or more laundry or cleaning additive materials, preferably including oxygen bleaching agents (wherein B%, balanced the composition expressed as a percentage is obtained by subtracting the weight of said components (a) and (b) from the total weight of the preparation and then expressing the result as a percentage of the total weight of the preparation).

The present invention also preferably relates to laundry or cleaning compositions comprising:

(a) an effective amount, preferably from 1 ppm to about 99.9%, more preferably from 0.1% to 25% of the bleach catalyst and / or organic percarboxylic acid;

(b) a catalytically effective amount, preferably from about 1 ppb to about 49%, of a transition metal bleach catalyst, said catalyst comprising a transition metal complex and a macropolycyclic ligand (preferably cross-bridged macropolycyclic ligand), wherein:

(1) said transition metal is 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 (II), Ni (II), Ni (III), Cu (I), Cu (II), Cu (III), Cr (II), Cr (III) , Cr (IV), 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 (2) said macropolycyclic ligand is selected from the group consisting of (i) a cross-bridged macropolycyclic ligand of formula (I) having a dentition of 4 or 5:

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

Rn '(iii) a cross-bridged macropolycyclic ligand of formula (III) having a dentition of 6 or 7: Rn'

Rn '

-DRn '/ ^G

A G Rn ^ / k \ IF \

V ^θ V / \

Rn '(III)

D '

E ^Z \ _n '

The Rri in these formulas is:

- each E is a group (CR _n ) _and -X- (CR _n ) _a ', wherein -X- is selected from the group consisting of O, S, NR and P, or a covalent bond, and preferably X is a covalent bond and for each E the sum of a + a 'is independently selected from 1 to 5, more preferably 2 and 3;

each G is a group (CR _n ) b;

each R is independently selected from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl (e.g. benzyl) and heteroaryl, or two or more R's are covalently bonded to form an aromatic, heteroaromatic, cycloalkyl or heterocycloalkyl ring;

· · · · * · * * * * · · · · · ·

14- · · · · · · · · · · · · ·

- each D is a donor atom independently selected from the group consisting of N, O, S and P, and at least two D atoms are bridged donor atoms coordinated to the transition metal (in preferred embodiments, all donor atoms are D, donor atoms coordinating to the transition metal, unlike heteroatoms in the structure that are not D as such that may be present in E; heteroatoms that are not D may be without coordination and indeed are always without coordination whenever present in preferred embodiments);

- B is a carbon atom or a D donor atom or a cycloalkyl or heterocyclic ring;

each n is an integer independently selected from 1 or 2, complementing the valency of the carbon atom to which the R unit is covalently attached;

each n is an integer independently selected from 0 or 1, complementing the valency D of the donor atom to which R is covalently bonded;

each n is an integer independently selected from 0, 1 and 2, complementing the valency of the B atom to which the R units are covalently bonded;

- each aaa 'is an integer independently selected from 0 to 5, preferably a + a' is 2 or 3, wherein the sum of all a plus a 'in the ligand of formula (I) ranges from about 6 (preferably from 8) to about 12, the sum of all a plus a 'in the ligand of formula (II) is in the range of 8 (preferably 10) to about 15 and the sum of all a plus a' in the ligand of formula (III) is in the range of 10 (preferably 12) to about 18;

each b is an integer independently selected from 0-9, preferably 0-5 (wherein when b = 0, (CR n) o represents a covalent bond) or in any of the above formulas one or more groups (CR n) b covalently bonded from D to B is absent if at least two (CR _n ) b covalently bind two of the donor atoms to B in the formula and the sum of all h is in the range of about 1 to 5; and (iii) optionally, one or more non-macropolycyclic ligands, and (c) one or more laundry or cleaning additive materials, preferably comprising an oxygen bleach at the appropriate concentrations as defined above.

The present invention preferably relates to detergents and cleaning compositions comprising:

(a) an effective amount, preferably from about 1 ppm to about 99.9%, more preferably from 0.1% to about 25% of the hydrophobic activator with bleach;

(b) a catalytically effective amount, preferably from about 1 ppb to about 99.9% of a transition metal bleach catalyst, said catalyst comprising a transition metal complex and a cross-bridged macropolycyclic ligand, wherein:

• ·

(1) said transition metal is selected from the group consisting of Mn (II), Mn (III), Mn (IV), Fe (II), Fe (III), Cr (II), Cr ( III), Cr (IV), Cr (V), and Cr (VI);

(2) said cross-bridged macropolycyclic containing:

the ligand is selected from the group of r (CR n) a

(AND)

in the following formulas:

each R is independently selected from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl (e.g. benzyl) and heteroaryl, or two or more R is covalently bonded to form an aromatic, heteroaromatic, cycloalkyl or heterocycloalkyl ring;

each n is an integer independently selected from 0, 1 and 2, complementing the valency of the carbon atom to which the R groups are covalently bonded;

each b is an integer independently selected from 2 and 3, and

- each a is an integer independently selected from 2 and 3, and (3) optionally, one or more non-macropolycyclic ligands and (c) at least 0.1%, preferably B%, of one or more laundry or cleaning additive materials, preferably comprising oxygenates bleaching agents (where B%, balanced composition expressed as a percentage is obtained by subtracting the weight of said components (a) and (b)

9 • 9

98 9 9 9 9 9 9 9

9 9 9 9 9 9 9 9 9 9 9 9

9 9 9 9 9 9

999 99 99999 99 9 9 from the total weight of the preparation and then expressing the result as a percentage of the total weight of the preparation).

The invention further relates to a method of cleaning fabrics or rigid surfaces, the method comprising contacting the fabric or rigid surface with a catalytically effective amount, preferably 0.01 ppm to 500 ppm of a transition metal bleach catalyst, which is a transition metal complex, and cross-bridged macropolycyclic ligand, with an effective amount, preferably from 1 ppm to about 10,000 ppm, more preferably from 10 ppm to about 5000 ppm of bleach activator and / or preformed organic peroxyacid, and preferably also an oxygen bleaching agent. The preferred method comprises contacting the fabric or hard surface with an oxygen bleach, a bleach activator and / or an organic percarboxylic acid and a transition metal bleach catalyst, wherein said transition metal bleach catalyst comprises a transition metal complex selected from the group consisting of Mn (II). ), Mn (III), Mn (IV), Fe (II), Fe (III), Fe (IV), Co (I), Co (II), Co (III), Ni (I) ), Ni (II), Ni (III), Cu (II), 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 (H), Ru (III) and Ru (IV), preferably Mn (II), Mn (III), Mn (TV), Fe (II), Fe (III), Cr (II), Cr (III), Cr (IV), Cr (V) and Cr (VI), preferably Mn, Fe and Cr in the oxidation state of (II) and (III), coordinated with a macropolycyclic rigid ligand, preferably a cross-bridged macropolycyclic ligand having at least 4 donor atoms, wherein at least two are p donor atoms řemostění.

The present invention also relates to methods of cleaning fabrics or solid surfaces, the method comprising contacting the fabric or rigid surface with a transition metal bleach catalyst, a complex as described above, a hydrophobic and / or hydrophilic bleach activator, and an oxygen bleaching agent.

All parts, percentages and ratios herein are by weight unless otherwise indicated. All documents cited herein are incorporated herein by reference.

Detailed description of the invention

Bleaching agents:

The compositions of the invention include a particularly selected transition metal bleach catalyst comprising a transition metal complex with a macropolycyclic rigid ligand, preferably a bridged ligand. The composition further comprises a hydrophobic and / or hydrophilic bleach activator (eg, sodium nonanoyloxybenzenesulfonate, Ν, Ν, Ν ', et'tetraacetylethylenediamine) and and / or an organic percarboxylic acid (e.g., magnesium monoperoxyphthalate hexahydrate, 1,12-diperoxydodecadioic acid, 6-nonanylamino-6-oxoperoxycaproic acid). The formulations also include at least one additive material, preferably comprising an oxygen oxidizing agent, preferably a low cost, readily available substance that produces no waste or produces very little waste as a source of hydrogen peroxide. The source of hydrogen peroxide may be H2O2 itself, solutions thereof or any hydrogen peroxide releasing salt, adduct or precursor such as sodium perborate, sodium percarbonate or mixtures thereof. Other sources of available oxygen such as peroxosulfate (e.g., OXONE, manufactured by DuPont) as well as organic peroxides are also useful.

For the sake of simplicity, organic percarboxylic acids and bleach activators are not included in the group of optional oxygen bleaching agents that are additional materials for the compositions and methods of the invention. However, mixtures of the oxygen bleaching agents with the bleach activators of the present invention are preferred. Furthermore, mixtures of oxygen bleaching agents and organic percarboxylic acids can be used, e.g. as a mixture of hydrogen peroxide and peracetic acid or a salt thereof.

More preferably, the additive component comprises both an oxygen bleaching agent and at least one additional additive material selected from the group of non-bleaching additives suitable for laundry detergents or cleaning products. Non-bleaching additives as defined herein are additives that are useful in detergents and cleaning products, which are not whitened or recognized as adjuncts used in cleaning primarily as bleach promoters such as bleach activators, organic bleach catalysts or organic percarboxylic acid of acids. Preferred non-bleaching additives include detersive surfactants, detergent binders, non-bleaching enzymes having useful function in detergents, and the like. Preferred compositions of the invention may comprise a source of hydrogen peroxide which is any salt of hydrogen peroxide releasing, such as sodium perborate, sodium percarbonate, and mixtures thereof.

When cleaning solid surfaces or washing laundry using the compositions of the present invention, the target material, i.e. the material to be cleaned, will typically be the surface of the fabrics soiled with eg various hydrophilic food residues such as coffee, tea or wine with hydrophobic stains such as they are fat stains, or they are dingy surfaces, eg yellowed by the presence of relatively unevenly dispersed fine residues of hydrophobic stains.

• · · · ·

Preferred detergents or cleaning compositions herein include:

(a) an effective amount, preferably from 1 ppm to about 99.9%, more preferably from 0.1% to about 25% of a bleach activator (hydrophobic or hydrophilic) and / or an organic percarboxylic acid;

(b) a catalytically effective amount, preferably from 1 ppb to about 99.9%, of a transition metal bleach catalyst which is a complex of a transition metal and a cross-bridged macropolycyclic ligand; and (c) one or more laundry or cleaning additive materials, preferably comprising an oxygen bleach at the levels described above.

Preferred laundry detergent compositions include adjuvants such as binders including zeolites and phosphates, surfactants such as anionic and / or nonionic and / or cationic surfactants, dispersion polymers (which modify and inhibit crystal growth of calcium and / or magnesium salts), chelants (which control the transition metals supplied by the wash water), alkalis (for pH adjustment) and detersive enzymes. Detergent or additive detergent compositions may additionally include one or more excipients, fillers, perfumes, conventional enzyme-containing particulate materials including enzyme cores or nonpareils, as well as pigments and the like. Additional ingredients such as soil release polymers, brighteners and / or color transfer inhibitors may be present in the preferred laundry compositions of the present invention.

The compositions of the present invention may include laundry detergents, solid surface cleaners, and the like, including all components required for cleaning, alternatively, the compositions may be made for use as cleaning accessories. For example, the cleaning adjunct may be a composition comprising a transition metal bleach catalyst, a bleach activator and / or organic percarboxylic acid, a detersive surfactant and a binder and may be sold for use as an adjunct which may be used with a conventional detergent comprising perborate, percarbonate or other. primary oxidant. The compositions of the present invention may include automatic dishwashing (ADD) compositions and tooth cleaners and are therefore generally not limited to laundry washing.

In general, the materials used to make the ADD compositions of the present invention are preferably tested for whether they form stains or films on glassware. Test methods for spotting and film formation are generally described in the literature for automatic dishwasher detergents, including DIN test methods. Certain oily materials, especially those having longer hydrocarbon chains and insoluble materials such as strengths, as well as long-chain fatty acids or soap suds, are excluded or limited from these preparations.

The amount of the basic ingredients may vary within wide limits, but preferred cleaning compositions of the present invention (1% aqueous solutions have a pH of from about 6 to about 13, more preferably from about 7 to about 11.5, and most preferably less than about 11, especially from about 7 to about 10). 5) are those comprising: from 1 ppb to about 99.9%, preferably from 0.01 ppm to about 49%, and typically from 0.01 ppm to about 500 ppm of a transition metal bleach catalyst in use; in accordance with the present invention; more typically from 0.1% to about 25%, and typically from 1 ppm to about 10,000 ppm of bleach activator and / or organic percarboxylic acid during use; and a balance typically from at least 0.01%, preferably from at least 51%, more preferably from 90% to about 100% of one or more laundry or cleaning additives. In preferred embodiments, from 0.1% to about 90%, preferably from about 0.5% to about 50%, of an oxygen bleaching agent such as preformed percarboxylic acids or preferably, may also be present (also expressed as a percentage by weight of the total composition). hydrogen peroxide sources; from 0% to about 20%, preferably at least 0.001% of a conventional bleach enhancing additive such as hydrophobic and / or hydrophilic bleach activators, and at least 0.001%, preferably from 1% to about 40%, of laundry or cleaning additives which do not a primary role in bleaching, such as a detersive surfactant, a detersive binder, a detergent enzyme, a stabilizer, a detergent buffer, or mixtures thereof. Suitably, these fully formulated embodiments contain from 0.1% to about 15% polymer dispersants, from 0.01% to about 10% chelant, and from about 0.00001% to about 10% detersive enzyme as regards non-bleaching additives, although they may other additional or supplementary components, in particular colorants, perfumes, proparfems (fragrance-releasing compounds after being exposed to an appropriate trigger such as heat, enzyme or pH changes) may be present. Preferred additives according to the invention are selected from the groups of bleach-stable substances, although bleach-unstable substances can often be included according to the experience of the formulator.

The detergent compositions of the present invention may have any desired physical form, when in the form of granules, the water content limit for the best storage stability thereof is less than 10%, preferably less than 7%.

Preferred compositions of the invention further include those that are substantially free of chlorinated bleaching agents. Essentially free of chlorinated bleaches means that the formulator does not intentionally add chlorine-containing bleaching agents such as •

ΙΟ ······ ·

Hypochlorite or its sources such as chlorinated isocyanurates. However, due to influences beyond the control of the formulator, such as chlorination of the wash water, a certain non-zero amount of chlorine may be present in the wash solution. The term substantially free may also be advantageously constructed with reference to the limitation of other components such as phosphate binders.

The term catalytically effective amount as used herein refers to the amount of transition metal bleach catalyst present in the composition of the invention or during use in the process of the invention that is sufficient under otherwise comparable use conditions to exhibit at least partial oxidation of the material to be treated. oxidation by the preparation or method.

When used in compositions or methods for washing or cleaning solid surfaces, a catalytically effective amount of a transition metal bleach catalyst is an amount sufficient to intensify the action on the soiled surface. In these cases, the effect is typically improved in one or more of the following features: whiteness, brightness and stain removal; a catalytically effective amount is one that requires less than the stoichiometric number of moles of catalyst as compared to the number of moles of an oxidant, such as hydrogen peroxide or peracid, required to produce a measurable effect. In addition to direct observation of the solid cleaned or bleached surface, the catalytic bleaching effect (where possible) can be measured indirectly, such as by measuring the kinetics or end products of the dye oxidation in solution.

As mentioned, the invention includes catalysts both at their concentrations during use and at concentrations that can be commercially provided for sale as concentrates; the catalytically effective amount thus includes both these concentrations at which the catalyst is highly diluted and ready for use, e.g. at ppb concentrations, as well as compositions having a somewhat higher concentration of catalyst, bleach activator and / or organic percarboxylic acid and additive material. Medium concentration formulations as summarized herein may include formulations comprising from 0.01 ppm to about 500 ppm, more preferably from 0.05 ppm to about 50 ppm, even more preferably from 0.1 ppm to about 10 ppm based catalyst. transition metal, and a balance of up to 100%, typically about 99% or more, being bleach activators and / or organic percarboxylic acid in solid or liquid form and supplementary materials (eg fillers, solvents and additives specially adapted for a particular application, such as detergents, additives and the like). Preferred concentrations for use in the compositions and methods of the invention are described below.

· · · • · · · · · in in in in in in in in in in in in in in in in in in in in · Iy ····· · · · · · · ···

When washing laundry, the target substrate will typically be a fabric soiled with, for example, various food residues. The test conditions will vary depending on the type of washing machine used and the user's habits. Thus, front-load washing machines used in Europe generally use less water and higher detergent concentrations than top-loading washing machines used in the US. Some washing machines have a considerably longer wash cycle than others. Some users choose to use very hot water, others use hot or even cold water for washing clothes. Of course, the catalytic efficiency of the transition metal bleach catalyst will be influenced by these effects, and the concentration of the transition metal bleach catalyst used in the fully formulated detergent and bleaching compositions can be adjusted accordingly. For practical reasons, not limitation, the compositions and methods of the present invention can be configured to provide a transition metal bleach catalyst concentration in the aqueous wash solution of the order of at least one ppb and the compositions will preferably provide from 0.01 ppm to about 500 ppm of a transition metal bleach catalyst in the wash solution, and further provide in the wash solution of the order of about 1 ppm to about 10,000 ppm, preferably from about 10 ppm to about 5000 ppm of bleach activator and / or organic percarboxylic acid.

An effective amount herein refers to an amount of material, such as detergent additives, which, under otherwise comparable conditions of use, is sufficient to provide the desired laundry performance and cleaning method while improving the appearance of the dirty surface in one or more duty cycles. For example, a duty cycle is one wash of a laundry package by a user. The appearance or visual effect may be measured by a consumer, a technical observer such as a trained professional, or by means of technical devices such as spectroscopy or imaging analysis. Preferred concentrations of additive materials for the compositions and uses of the invention are described below.

Transition metal bleach catalysts:

The compositions of the invention include a transition metal bleach catalyst. Generally, the catalyst comprises at least partially covalently bonded transition metal to which is attached at least one particularly defined macropolycyclic rigid ligand, preferably having four or more (preferably 4 or 5) donor atoms, and which is cross-bridged or otherwise bound such that macrocyclic the ring complexes the metal in a folded conformation. Thus, the catalysts of the present invention are not derived from conventional types of macrocycles, such as porphyrin complexes, in which the metal readily assumes a square flame configuration, nor are those in which the metal is fully enclosed within ligands. Instead, the catalysts useful in the present invention are selected from a variety of complexes, previously unknown, having a transition state in which the metal is bound in the cavity. Further, one or more ligands of generally conventional types such as chlorides covalently bonded to the metal may be present in the catalyst and, if desired, one or more counterions, most often anions such as chloride, hexafluorophosphate, perchlorate and the like, and other molecules to fill the crystal formation as desired, such as crystalline water. In general, only the transition metal and the macropolycyclic ligand are necessary.

The transition metal bleach catalyst useful in the present invention may generally contain known substances as long as they are within the definition of the invention, as well as more preferably any of a large number of novel compounds designed specifically for use in laundry or cleaning operations, as illustrated in the following list, which is not intended to be limiting:

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)

Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) hexafluorophosphate Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] manganese hexadecane (III) Diaquo-4,10-dimethyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane manganese (II) hexafluorophosphate Diaquo-5,12-dimethyl-1,5,8,12- tetraazabicyclo [6.6.2] hexadecane manganese (II) tetrafluoroborate Diaquo-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] manganese hexadecane (III) hexafluorophosphate Dichloro-5,12-di-n-butyl-1,5,8,12-tetraazabicyclo [6.6.2] manganese hexadecane (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] manganese hexadecane (II)

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

Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] manganese hexadecane (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] iron tetradecane (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] copper tetradecane (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] manganese hexadecane (II) Dichloro-4,10-dimethyl-3,8-diphenyl-1,4,7,10-tetraazabicyclo [5.5.2] manganese tetradecane (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 (H) Dichloro-2,2,4,5,9,11,1 1,12-octamethyl-1,5,8,12 -tetraazabicyclo [6.6.2] manganese hexadecane (II) Dichloro-3,3,5,10,10,12-hexamethyl-1,5,8,12-tetraazabicyclo [6.6.2] manganese hexadecane (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] manganese hexadecane (II) Dichloro-1,5,8,12-tetraazabicyclo [6.6.2] manganese hexadecane (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)

Aquo-chloro-2- (2-hydroxyphenyl) -5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II)

Aquo-chloro-10- (2-hydroxybenzyl) -4,10-dimethyl-1,4,7,10-tetraazabicyclo [5.5.2] manganese tetradecane (II)

Chloro-2- (2-hydroxybenzyl) -5-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecan 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) Dichloro-5- (2-sulfato) dodecyl-12-methyl-1 chloride; 5,8,12-tetraazabicyclo [6.6.2] manganese hexadecane (II) Aquo-chloro-5- (2-sulfato) dodecyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] manganese hexadecane (III)

Aquo-chloro-5- (2-sulfato) dodecyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II)

Aquo-chloro-5- (3-sulfonylpropyl) -12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) · «· · · · · · · · • · • • • • • • • •

Dichloro-5- (trimethylaminopropyl) 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-tetraazabicyclo [8.6.6] docosa-3 (8), 4,6-triene manganese (II) Dichloro-4,1 l-dimethyl-1,4 7.1 l-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 (fl)

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

Diaquo-3,10-dicarboxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] manganese hexadecane (II) Chloro-20-methyl-1,9,20,24,25-pentaazatetracyclo [7.7.7.1 ^3,7 1 ^11,15 .] Pentacose 3,5,7 (24), 11,13,15 (25) -hexane manganese (II) hexafluorophosphate

Trifluoromethanesulfonate-20-methyl-9,20,24,25-pentaazatetracyklo [7.7.7.1 ^{3 '7} .l ^11.15.] Pentakosa3,5,7 (24), 11,13,15 (25) -hexaen manganese (II) trifluoromethanesulfonate

Trifluoromethanesulfonate-20-methyl-9,20,24,25-pentaazatetracyklo [7.7.7.1 ^{3 '7} .1 ^11,15.] Pentakosa3,5,7 (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

Preferred complexes useful as transition metal bleach catalysts further generally include not only monometallic mononuclear species such as those described above, but also bimetallic, trimetallic or cluster types, especially when polymetallic types are chemically transformed in the presence of primary oxidants to form mononucleic monometallic active particles. Monometallic mononuclear complexes are preferred. As defined above, the transition metal monometallic bleach catalyst comprises only one transition metal atom per mole of complex. A monometallic mononuclear complex is one in which any donor atom of the base macrocyclic ligand is bound to the same transition metal atom, i.e., the base ligand does not "bridge" one or more transition metal atoms.

Transition catalysts

Just as the macropolycyclic ligand cannot be infinitely variable for the purposes of this invention, it is similar to metal. An important part of the invention is to achieve a match between the choice of ligand and the choice of metal which would lead to an excellent bleach catalyst. In general, the transition metal bleach catalysts of the present invention include transition metals selected from the group consisting of Mn (II), Μη (ΙΠ), Mn (IV), Mn (V), Fe (II), Fe (III), Fe (IV) ), Co (II), Co (II), Co (II), Ni (I), Ni (II), Ni (II), Cu (I), Cu (II), Cu (II), Cr (II) ), Cr (III), Cr (IV), Cr (VI), Cr (VI), V (III), V (TV), V (V), Mo (IV), Mo (V), Mo (VI) ), W (IV), W (VI), W (VI), Pd (II), Ru (II), Ru (III) and Ru (IV).

Preferred transition metals in the transition metal bleach catalysts of the present invention include manganese, iron and chromium, preferably Mn (II), Mn (III), Mn (IV), Fe (II), Fe (III), Cr (II) ), Cr (III), Cr (IV), Cr (V) and Cr (VI), more preferably manganese and iron, most preferably manganese. Preferred oxidation states include the oxidation state (II) and (ΙΠ). Manganese (II) is included in both the low and high spin configuration. It should be noted that complexes such as low-spin Mn (II) are somewhat rare throughout coordination chemistry. The designation (II) or (III) means that the coordinated transition metal has a corresponding oxidation state, the coordinated metal ion is not a free ion or an ion having only water as a ligand.

Ligandy

Generally, the term "ligand" means any group capable of direct covalent association with a metal ion. Ligands can be charged or neutral and can range from simple monovalent donors such as chlorides or simple amines, which form a single coordinated bond and are attached to the metal at one point, to oxygen or ethylene, which can form three-membered rings with metal and thus can be said to have point-to-point attachment up to large units such as ethylenediamine or azamacrocycles, forming the maximum number of single bonds with one or more metals, the number of which depends on available metal binding sites and the number of free pairs or alternating free binding sites ligand. Numerous ligands can form non-single donor bonds and can be attached at several sites.

9 9

Ligands useful according to the invention fall into several groups: basic macropolycyclic rigid ligands, preferably cross-bridged macropolycycles (preferably there will be one such ligand in useful transition metal complexes, but more eg two ligands may be present, but not in preferred complexes) ; other optional ligands, which are generally other than the basic macropolycyclic rigid ligands (generally there will be from 0 to 4, preferably from 1 to 3 such ligands), and ligands connected temporarily to the metal as part of the catalytic cycle, these typically related to water, hydroxide, oxygen or peroxides. Ligands of this third group are not necessary to define a bleaching metal catalyst that is a stable, isolatable chemical compound that can be fully characterized. A ligand that binds to the metal via donor atoms, each having at least one free electron pair usable for donating to the metal, has a donor ability or potential dentition at least equal to the number of donor atoms. Generally, this donor ability may be exercised in whole or in part.

Macropolycyclic rigid ligands

A macropolycyclic ligand is necessary to achieve transition metal catalysts. This is coordinated (covalently linked to any of the above-mentioned transition metals) by three, preferably at least four and most preferably four or five donor atoms to the same transition metal.

In general, the macropolycyclic rigid ligands of the present invention can be viewed as a result of adding additional structural rigidities to specifically selected "parent macrocycles". The term "rigid" has been defined as a forced change in flexibility: see D. H. Busch., Chemical Reviews., (1993), 93, 847-860, incorporated herein by reference. More specifically, "rigid" means that the base ligand that is suitable for the purposes of the present invention must be visibly more rigid than the macrocycle ("parent macrocycle") that is otherwise identical (having the same ring size and type and number of atoms in the main cycle) however, it lacks the superstructure (especially the linker or preferably bridging unit) of the ligand. In determining the relative rigidity of macrocycles with and without superstructures, those skilled in the art will use free forms (not metal bound) of macrocycles. It is well known that rigidity is useful in comparing macrocycles, suitable means for determining, measuring, or comparing rigidity include computational methods (see, eg, Zimmer, Chemical Reviews, (1995), 95 (38), 2629-2648 or Hancock et al. ., Inorganica Chimica Acta, (1989), 164, 73-84 Determining whether one macrocycle is more rigid than another can often be accomplished simply by constructing a molecular model, so it is generally not necessary to know the configuration energies in absolute values or is accurate Excellent comparative comparisons of rigidity of one macrocycle to another can be made using inexpensive computing programs designed for personal computers such as ALCHEMY III, commercially available from Tripos Associates, and Tripos also delivers more expensive software allowing not only comparison but also absolute determination, alternatively, SHAPES may be used (see Zim One observation that is important in the context of the present invention is that it is optimal for the purposes of the present invention that the parent macrocycles are significantly more flexible than the bridged form. Thus, unexpectedly, it is preferred to use parent macrocycles containing at least four donor atoms, such as cyclamic derivatives, and to bridge them, rather than starting with a more rigid parent mycrocycle. It has further been found that cross-bridged macrocycles are significantly preferred over other bridged macrocycles.

However, the macrocyclic rigid ligands of the invention are not limited to those synthesized from any preformed macrocycles plus a preformed "rigidizing" or "conformation-modifying" element; rather, a wide variety of synthetic compositions are useful, such as template synthesis. See. e.g., Busch et al., in "Heterocyclic Compounds: Aza-crown Macrocycles", J. S. Bradshaw et al., supra, referring to synthetic methods.

According to one aspect of the invention, the macropolycyclic rigid ligands include those comprising:

(i) 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 by covalent linkages of at least one, preferably 2 or 3 non-donor atoms, two to five (s) preferably three to four, more preferably four) of these atoms are coordinated to the same transition metal complex, and (ii) a linker, preferably a cross-bridging chain, covalently linking at least 2 (preferably non-adjacent) donor atoms of the organic macrocyclic ring, covalently bonded (preferably non-adjacent) donor atoms are bridged by donor atoms coordinated to the same transition metal in the complex and wherein said linker (preferably cross-linking chain) comprises from 2 to about 10 atoms (preferably is cross-linking chain) · Selected from 2, 3, or 4 non-donor atoms and 4-6 non-donor atoms with another donor atom).

In preferred embodiments of the invention, the cross-bridged macropolycycle is coordinated by four or five nitrogen donor atoms to the same transition metal. These ligands include:

(i) an organic macrocyclic ring containing four or more donor atoms selected from N and optionally O and S, wherein at least two of these atoms are N (preferably at least 3, more preferably at least 4 of these atoms are N) separated from each other by a covalent by linking 2 or 3 non-donor atoms, wherein two to five (preferably three to four, more preferably four) of these atoms are coordinated to the same transition metal in the complex;

(ii) a cross bridging chain that covalently connects at least two non-donor N atoms of an organic macrocyclic ring, wherein said covalently linked non-adjacent N donor atoms are bridged by N donor atoms that are coordinated to the same transition metal complex and wherein said cross bridging chain comprises 2 up to about 10 atoms (preferably the cross-bridging chain is selected from 2, 3 or 4 non-donor and 4-6 non-donor atoms with another, preferably N, donor atom).

While the invention is clear from the foregoing description and illustrations, certain terms may be further defined and illustrated in the practice of the invention. As used herein, the term "macrocyclic rings" refers to covalently linked rings formed from four or more donor atoms (i.e., heteroatoms such as nitrogen or oxygen) with the carbon chain linking them, and any macrocyclic ring as defined herein must contain a total of at least ten, preferably at least twelve atoms in the macrocyclic ring. The macropolycyclic rigid ligand of the invention may contain more than one ring of any kind in the ligand, but at least one macrocyclic ring must be identifiable. In addition, in a preferred embodiment of the invention, the two heteroatoms are not linked directly. Preferred transition metal bleach catalysts are those wherein the macropolycyclic ligand comprises an organic macrocyclic ring (main ring) containing at least 10-20 atoms, preferably 12-16 atoms, more preferably from about 12 to 20 atoms, most preferably from 12 to 20 atoms. 16 atoms.

Further, in preferred compounds of the present invention, a "macrocyclic ring" refers to covalently bonded rings formed from four or more donor atoms selected from N and, optionally, N and optionally. ·· · * ·· · · · · · ···

...... ·· ··· ·· ··· ·· ·· ··

O and S, wherein at least two of these donor atoms are N with the C2 or C3 carbon chains connecting them and any macrocyclic ring as defined herein must contain at least twelve atoms in the macrocyclic ring. The cross-bridged ligand may contain more than one ring of any kind in the ligand, but at least one macrocycle must be identifiable in the cross-bridged macropolycycle. In addition, unless otherwise stated, no two heteroatoms can be linked directly. Preferred transition metal bleach catalysts are those wherein the cross-bridging macropolycyclic ligand comprises an organic macrocyclic ring containing at least 12 atoms, preferably from 12 to about 20 atoms, most preferably 12 to 16 atoms.

"Donor atoms" in the present invention refer to nitrogen, oxygen, phosphorus or sulfur (preferably N, O and S) which, when incorporated into the ligand, still have one free electron pair available to form a donor-acceptor bond with the metal. Preferred transition metal bleach catalysts are those wherein the donor atoms in the organic macrocyclic ring of the cross-bridged macropolycyclic ligand are selected from the group consisting of N, O, S and P, preferably N and O, and most preferably all N. Also preferred are cross-linked bridged macropolycyclic ligands containing 4 or 5 donor atoms, all coordinated to the same transition metal. The most preferred transition metal bleach catalysts are those in which the macropolycyclic ligand contains 4 nitrogen donor atoms, all coordinated to the same transition metal, and those in which the cross-bridged macropolycyclic ligand comprises 5 nitrogen atoms, all coordinated to the same transition metal.

The non-donor atoms of the macropolycyclic ligand of the present invention are most commonly carbons, although a plurality of atomic types may be included, especially in the possible exocyclic substituents (as pendant groups, illustrated below) of mycrocycles, which are neither necessary nor essential for the metal catalyst. In the broadest sense, the term non-donor atoms can refer to any atom that is not necessary to form donor bonds to the metal in the catalyst. Examples of such atoms may include heteroatoms such as sulfur involved in the coordination of incapable sulfonate groups, phosphorus in the form of phosphonium salt groups, phosphorus in the form of P (V) oxide, transition metals and the like. In some embodiments, all non-donor atoms are carbon.

The term macropolycyclic ligand is used herein to describe the base ligand required to form the parent metal catalyst. As the name implies, · · · · · · · · «• • • • • • • • • • • • jméno jméno jméno jméno jméno jméno jméno jméno Such a ligand is both macrocyclic and polycyclic. Polycyclic means that it is least bicyclic in the usual sense. The basic macropolycyclic ligands must be rigid and the preferred ligands are cross-bridged.

Non-exhaustive examples of macropolycyclic rigid ligands as defined herein include 1.3-1.6:

Ligand 1.3 is a mycropolycyclic rigid ligand in accordance with the present invention, which is a highly preferred cycla derivative that is cross-bridged, substituted with methyls (all nitrogen atoms are tertiary). Formally, this ligand is named 5,12-dimethyl-1,5,8,12-tetraazabycyclo [6.6.2] hexadecane, using the extended von Bayer system. See. A Guide to IUPAC Nomenclature of Organic Compounds: Recommendations 1993; R. Panico; W. H. Powell; and J. C. Richer (Eds.), Blackwell Scientific Publications, Boston, 1993; see in particular section R-2.4.2.1. According to conventional terminology, N 1 and N 8 are bridged atoms, as defined above, more particularly donor bridged atoms because they have free pairs capable of donating to the metal. N1 is attached to two non-bridged atoms, N5 and NI2, by means of different carbon chains 2,3,4 and 14,13 to the N8 bridge atom via the linking group a, b, which is the saturated carbon chain of two carbon atoms here. N8 is attached to two non-bridged donor atoms N5 and N12 by different chains 6,7 and 9,10,11. The chain a, b is a linker as defined above and is a special preferred type referred to as a cross-bridging unit. The macrocyclic ring of the ligands alone or otherwise the main ring (IUPAC) includes all four donor atoms and chains 2,3,4; 6.7; 9,10,11 and 13,14 but not a, b. This ligand is conventionally bicyclic. The short bridge or link unit a, b is a cross bridging as defined above, bisecting a macrocyclic ring.

• · ·

1.4

Ligand 1.4 falls within the general definition of macropolycyclic ligands as defined above, but is not a preferred ligand because it is not a bridged bridge as defined above. In particular, the linker unit a, b connects adjacent donor atoms N1 and NI2, which is outside the preferred embodiment of the present invention: cf. for comparison, a prior macrocyclic rigid ligand in which the linker unit a, b is cross-bridging and joins non-adjacent donor atoms.

Ligand 1.5 falls within the general definition of a macropolycyclic rigid ligand given above. The ligand may be viewed as a main ring, which is a tetraazamacrocycle having three linking donor atoms. This macrocycle is bridged by a linker having a structure more complex than just a single chain because it contains a secondary ring. The linker includes both a cross-bridging binding mode and a non-cross-bridging binding mode.

1.6

Ligand 1.6 falls within the general definition of mycropolycyclic rigid ligands. Five donor atoms are present, two of which are bridged donor atoms. This ligand is a preferred cross-bridged ligand. It contains no exocyclic or pendant substituents with aromatic content.

In contrast, for comparison purposes, the following ligands (1.7 and 1.8) neither meet the broad definition of the mycropolycyclic rigid ligand of the present invention nor fall within the preferred group of cross-bridged substances and are therefore completely outside the scope of the invention.

1.7

There is no nitrogen atom bridging the donnor atom in the ligand itself. There are not enough donor atoms.

The ligand itself is also outside the invention. Nitrogen atoms are not bridging donor atoms and the double carbon bond between the two main rings does not meet the definition of the linking unit of the present invention because, instead of joining through a single macrocyclic ring, it connects two different rings. Thus, the linkage does not increase rigidity within the meaning of the term macropolycyclic rigid ligand. See also the definition of the coupling unit given in the present invention.

In general, basic mycropolycyclic rigid ligands (and corresponding transition metal catalysts) include:

(a) at least one macrocyclic backbone comprising four or five heteroatoms (b) a covalently linked nonmetallic superstructure capable of increasing the rigidity of the macrocycle, preferably selected from (i) a bridging superstructure such as a linker unit

9 9 9 99 9

9 9 9 9 9 9 9

9,999 9,999,999 9 9 9

9 9 9 9 9 9

(9) a cross-bridging superstructure, such as a cross-bridging linker (iii) a combination thereof.

The term superstructure is used as in the definition of Busch et al. in the Chemical Reviews article incorporated herein by reference.

Preferred superstructures of the present invention not only enhance the rigidity of the parent macrocycle, but also favor folding of the macrocycle to coordinate metal in the cavity. Suitable superstructures may be significantly simple, eg, couplers such as those illustrated in 1.9 and 1.10 may be used.

\ 19 ^ _(CH2) / where N is an integer, e.g. 2 to 8, preferably less than 6, typically 2 to 4 or (CH _{2) m} I

T ^- U '( ^CH 2) n

1.10 wherein m and n are integers from 1 to 8, more preferably from 1 to 3; Z is N or CH; and T is a compatible substituent such as H, alkyl, trialkylammonium, halogen, nitro, sulfonate or the like. The aromatic ring in 1.10 can be replaced by a saturated ring in which the Z atom attached to the ring can be N, O, S or C.

Without being limited by theory, it is believed that the preorganization introduced into the macropolycyclic ligands of the present invention, which leads to extra kinetic and / or thermodynamic stability of their metal complexes, is due to their topological stress or increased rigidity (loss of flexibility) , compared to a parent macrocycle that does not have superstructure. Macropolycyclic rigid ligands as defined herein, and their preferred cross-bridged subgroup, which can be said to be ultra-rigid, combine two sources of fixed preorganization. In preferred ligands of the invention, the linker and the parent macrocyclic ring are combined to form ligands having an excellent folding rate, typically higher than many known superstructured ligands in which the superstructure is attached to a predominantly flame, often unsaturated macrocycle. See. e.g., D. H. Busch, Chemical Reviews, (1993), 93, 847-880. Furthermore, preferred ligands have a number of certain properties, including (1) characterized by a very high affinity for protons, such as in a so-called proton sponge; (2) tend to react slowly with multivalent transition metals, which in combination with (1) makes it difficult to synthesize their complexes with some hydrolysable metal ions in hydroxyl solvents; (3) when coordinated to a transition metal atom as defined above, the ligands result in complexes having exceptional kinetic stability, such that metal ions dissociate very slowly under conditions that would otherwise break complexes with normal ligands; and (4) these complexes have exceptional thermodynamic stability; however, the unusual kinetics of the dissociation of ligands and transition metal may hinder conventional equilibrium measurements that quantify this property.

Other useful but more complex superstructures suitable for the purposes of the present invention include those that include an additional ring, as in 1.5. Other binding superstructures added to macrocycles include, for example, 1.4. In contrast, cross-bridged superstructures unexpectedly improve the suitability of using macrocyclic ligands for use as oxidation catalysts: the preferred cross-bridged super structure is 1.3. The superstructure showing a bypass in combination with a cross bypass is 1.11:

In 1.11, the coupling unit (i) is a cross bridging, while the coupling unit (ii) is not. 1.11 is less preferred than 1.3.

More generally, the linking unit as defined above is a covalently linked unit comprising a plurality of atoms having at least two points of covalent attachment to the macrocyclic ring and which do not form part of the main ring or rings of the parent mycrocycle. In other words, with the exception of linkages formed by attachment to the parent macrocycle, the linker is entirely in the superstructure.

In a preferred embodiment of the invention, the cross-bridged macropolycycle is coordinated by four or five donor atoms to the same transition metal. These ligands include:

(i) 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 by covalent linkages of 2 or 3 non-donor atoms, with two to five (preferably * 99 * Three to Four * 99 * · · · · · V · ♦ · V tři tři tři tři tři tři až až až až až more preferably four) of these donor atoms are coordinated to the same transition metal in the complex; and (ii) a cross bridging chain that covalently connects at least two non-adjacent organic macrocyclic ring atoms, said covalently linked non-adjacent donor atoms are donor bridging atoms that are coordinated to the same transition metal in the complex, and wherein said cross-bridging chain comprises from 2 to about 10 atoms (preferably the cross-bridging chain is selected from 2, 3 or 4 non-donor atoms and 4-6 non-donor atoms with another donor atom).

The term "bridged" or "bridged" refers to a covalent ligation, halving or bonding of a macrocyclic ring in which the two macrocyclic ring donor atoms are covalently linked by a linker, eg, another chain different from the macrocyclic ring, and further preferably wherein at least one donor atom (preferably an N donor atom) of the macrocyclic ring in each of the macrocyclic ring compartments, separated by ligation, halving or bonding. Cross bridging is not in molecule 1.3, where the two donor atoms of the preferred macrocyclic ring are joined in such a way that there are no donor atoms in each compartment. However, assuming cross bridging is present, any other bridging may be added and the bridged macrocycle will retain the preferred property of being cross-bridged: see FIG. structure 1.11. Thus, a cross-bridged or cross-bridged chain as defined above is a highly preferred type of linking unit comprising multiple atoms having at least two covalent attachment points to the macrocyclic ring and not forming part of the original macrocyclic ring (the main ring) and which is further joined to the new circle using the rule described when defining the term bridging.

The term adjacent to donor atoms in the macrocyclic ring indicates that there are no intervening donor atoms between the first and the next donor atoms in the macrocyclic ring; all intervening ring atoms present are non-donor atoms, typically carbon atoms. The complementary term non-contiguous refers to the donor atoms of the macrocyclic ring that there is at least one intervening donor atom between the first and the other donor atoms. In preferred instances, such as cross-bridged tetraazamacrocycles, there will be at least one pair of non-adjacent donor atoms that are bridged atoms and one pair of bridged atoms.

• ·

• · ·

The bridged atoms of the invention are macropolycyclic ligand atoms that are attached to the structure of the macrocycles in such a way that each non-donor bond to that atom is a single bond by forging and there are enough covalent single bonds to attach the atom designated as bridged in such a way that two rings, this number being the maximum that can be observed by visual inspection of an uncoordinated ligand.

In general, the metal bleach catalyst of the present invention may contain bridged atoms, which are carbons, but it is important that in some embodiments of the invention all the basic bridged atoms are heteroatoms, all heteroatoms being tertiary and all coordinated via free pairs to the metal. Preferred transition metal bleach catalysts of the present invention must contain at least two N bridged atoms and each coordinate to the metal via a free pair. Thus, bridged atoms are a point of attachment not only for macrocycle rings but also chelating rings.

The term additional donor atom, unless specifically indicated, means a donor atom other than the donor atom contained in the macrocyclic ring of the basic macropolycycle. E.g. the additional donor atom may be present in an optional exocyclic substituent of the macrocyclic ligand or in its cross-bridged chain. In some preferred embodiments, the additional donor atom is present only in the cross-bridged chain.

The term coordinated to the same transition metal is used to emphasize that a particular donor atom or ligand does not bind to two or more different metal atoms, but only one.

Optional ligands

It will be appreciated that transition metal bleach catalysts useful in the present invention may contain other non-macropolycyclic ligands, which may optionally be coordinated to the metal to fill the coordination number of the complexed metal. Such ligands may have any number of atoms capable of delivering electrons to the catalyst complex, but preferred ligands have a dentition of 1-3, preferably 1. Examples of such ligands are H ₂ O, ROH, NR ₃ , RCN, OH ', OOH', RS, RO ', RCOO', OCN ', SCN', N ₃ ', CN', F, d ', Br', Γ, O ₂ , NO ₃ ', NO ₂ ', SO4 ² ', SO ₃ ² ', PO4 ³ organic phosphates, organic phosphonates, organic sulphates, organic sulphonates and aromatic N donors such as pyridines, pyrazines, pyrazoles, imidazoles, benzimidazoles, pyrimidines, triazoles and thiazoles wherein R is H, optionally alkyl, optionally substituted aryl. Preferred transition metal bleach catalysts include one or two non-macrocyclic ligands.

The term non-macropolycyclic ligands is used herein to refer to ligands, such as those described above, which are generally not necessary for the formation of the metal catalyst and which are not cross-bridged macropolycycles. Not necessary in connection with macropolycyclic ligands means that in the broadly defined invention they may be substituted with a number of other conventional ligands. In a highly preferred embodiment of the invention, the mycropolycyclic and non-macropolycyclic ligands are finely balanced into a transition metal bleach catalyst, of course, there may be significant differences in performance when the indicated non-macropolycyclic ligands are replaced by other, especially ligands not illustrated herein.

The term metal catalyst or transition metal bleach catalyst is used to denote the parent catalyst compound of the invention and is commonly used with a metal candidate. It will be appreciated that the invention relates to optional catalytic materials. The term bleach catalyst may be used unqualified to refer to an organic catalyst material (without metal) or to an optional metal-containing catalyst that lacks the advantages of the base catalyst: such optional materials include, for example, known metalloporphyrins or metal-containing photobleaches. Other possible catalyst materials include enzymes.

Cross-bridged macropolycyclic ligands contain.

(i) a cross-bridged macropolycyclic ligand of formula (I) having a dentition of 4 or 5:

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

• · • ·

(Π) (iii) a cross-bridged macropolycyclic ligand of formula (III) having a dentition of 6 or 7:

Rrí

(III)

The Rff in these formulas is:

- each E is a group (CR _n ) _and -X- (CR _n ) a ', wherein -X- is selected from the group consisting of O, S, NR and P, or a covalent bond, and preferably X is a covalent bond and for each E the sum of a + a 'is independently selected from 1 to 5, more preferably 2 and 3;

each G is a group (CR n) b;

each R is independently selected from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl (e.g. benzyl) and heteroaryl, or two or more R's are covalently bonded to form an aromatic, heteroaromatic, cycloalkyl or heterocycloalkyl ring;

- each D is a donor atom independently selected from the group consisting of N, O, S and P, and at least two D atoms are bridged donor atoms coordinated to the transition metal (in preferred embodiments, all donor atoms are D, donor atoms coordinating to the transition metal, unlike heteroatoms in the structure that are not D as such that may be present in E; heteroatoms that are not D may be without coordination and indeed are always without coordination whenever present in preferred embodiments);

- B is a carbon atom or a D donor atom or a cycloalkyl or heterocyclic ring;

each n is an integer independently selected from 1 or 2, complementing the valency of the carbon atom to which the R unit is covalently attached;

each n is an integer independently selected from 0 or 1, complementing the valency D of the donor atom to which R is covalently bonded;

each n is an integer independently selected from 0, 1 and 2, complementing the valency of the B atom to which the R units are covalently bonded;

- each aaa 'is an integer independently selected from 0 to 5, preferably a + a' is 2 or 3, wherein the sum of all a plus a 'in the ligand of formula (I) ranges from about 6 (preferably from 8) to about 12, the sum of all a plus a 'in the ligand of formula (II) is in the range of 8 (preferably 10) to about 15 and the sum of all a plus a' in the ligand of formula (III) is in the range of 10 (preferably 12) to about 18;

each b is an integer independently selected from 0-9, preferably 0-5 (wherein when b = 0, (CR _n ) o represents a covalent bond) or in any of the above formulas, one or more groups (CR _n ) b covalently bonded from D to B are absent if at least two (CR _n ) b covalently bind two of the donor atoms to B in the formula and the sum of all b ranges from about 1 to about 5.

Preferred transition metal bleach catalysts wherein the cross-bridged macropolycyclic ligands D and B are selected from the group consisting of N and O and preferably D are N. Also preferred are those wherein in the cross-bridged macropolycyclic ligand are all and independently selected from integers 2. and 3, all X are selected from covalent bonds, all a are 0 and all b are independently selected from the integers 0, 1 and 2. Tetradentate and pentadentate cross-bridged macropolycyclic ligands are most preferred.

Unless otherwise specified, a convention describing dentition as used herein, such as in a mycropolycycle having a dentition of four, describes ligand characterization: namely, the maximum number of donor bonds that are capable of forming in coordination with a metal. Such a ligand is identified as tetradentate. Similarly, a mycropolycycle containing five nitrogen atoms, each with a free electron pair, is described as pentadentate. The present invention relates to bleaching compositions wherein the macropolycyclic rigid ligand exhibiting full dentition is in transition metal catalyst complexes; in addition, the invention also addresses any equivalent that may arise, for example, when one or more donor sites are directly coordinated with a metal. This can happen, for example, when •

9 9 9 · · ··

9 9 9 9 9 9 9 9 9 9 · 99 9 9 · ···· · · · · · ···

9 9 9 9 9 9

* Pentadentate ligand coordinated through four donor atoms to the transition metal and one donor atom is protonated.

Preferred bleaching compositions comprising a metal catalyst wherein the cross-bridged macropolycyclic ligand is a bicyclic ligand, preferably the cross-bridged macropolycyclic ligand is a mycropolycyclic group of formula (I), having the formula:

wherein each a is independently selected from the integers 2 or 3 and each b is independently selected from the integers 0,1 or 2.

Further preferred are macropolycyclic ligands selected from the group consisting of:

r (CR n) a

(CRn) a

in the following formulas:

• · • ·

each R is independently selected from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl (e.g. benzyl) and heteroaryl, or two or more R is covalently bonded to form an aromatic, heteroaromatic, cycloalkyl or heterocycloalkyl ring;

each n is an integer independently selected from 0, 1 and 2, complementing the valency of the carbon atom to which the R groups are covalently bonded;

each b is an integer independently selected from 2 and 3, and

each a is an integer independently selected from 2 and 3.

Further preferred are cross-bridged macropolycyclic ligands having the formula;

in this formula:

- each n is an integer independently selected from 1 or 2, complementing the valency of the carbon atom to which they are covalently bonded,

each of R ¹ and R ¹ 'is independently selected from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl (e.g. benzyl) and heteroaryl, or R 1 and / or R ¹ are covalently bonded to form an aromatic, heteroaromatic, cycloalkyl or heterocycloalkyl ring and wherein R is preferably H and R ¹ independently selected from linear or branched, substituted or unsubstituted C 1 -C 20 alkyl, alkenyl or alkynyl;

each a is an integer selected independently from 2 or 3;

preferably all nitrogen atoms in the cross-bridged macropolycyclic ring are coordinated to the transition metal.

Another preferred subset of transition metal complexes useful in the compositions and methods of this invention include the Mn (II), Fe (II) and Cr (II) complexes with a ligand having the formula:

• · · · · ·

wherein m and n are integers from 0 to 2, p is an integer from 1 to 6, preferably m and n are both 0 or both 1 (preferably both 1) or m is 0 and n is at least 1; and p is 1; and A is a non-aromatic hydrogen unit, in particular each A may be independently different and is preferably selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, C 5 -C 20 alkyl and one but not both of the A units is benzyl and combinations thereof. In one such complex, A is methyl and one A is benzyl.

This includes preferred cross-bridged macropolycyclic ligands having the formula:

wherein R ¹ is independently selected from H and linear or branched, substituted or unsubstituted C 1 -C 20 alkyl, alkenyl or alkynyl, and preferably all of the nitrogen atoms in the macropolycyclic rings are coordinated to the transition metal.

Also preferred are cross-bridged ligands having the formula:

in this formula:

• * • ·

each n is an integer independently selected from 1 or 2, complementing the valency of the carbon to which R is covalently bonded;

each of R ¹ and R ¹ 'is independently selected from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl (e.g. benzyl) and heteroaryl, or R 1 and / or R ¹ are covalently bonded to form an aromatic, heteroaromatic, cycloalkyl or heterocycloalkyl ring and wherein R is preferably H and R ¹ independently selected from linear or branched, substituted or unsubstituted C 1 -C 20 alkyl, alkenyl or alkynyl;

each a is an integer selected independently from 2 or 3;

preferably all nitrogen atoms in the cross-bridged mycropolycyclic ring are coordinated to the transition metal.

This includes preferred cross-bridged macropolycyclic ligands having the formula:

wherein in any formula R ^{1 is} independently selected from H or preferably linear or branched, substituted or unsubstituted C 1 -C 20 alkyl, alkenyl, or alkynyl, and preferably all nitrogen atoms in the macropolycyclic ring are coordinated to the transition metal.

The present invention has numerous variations and various embodiments, which, however, do not depart from the spirit and scope of the invention. The macropolycyclic ligand may be replaced by any of the following in the formulations of this invention:

In the above formulas, R, R ', R and R' may be, for example, methyl, ethyl or propyl. (Please note that in the above formalism, a short comma attached to an N denotes a methyl group).

• · *

While the above illustrative structures include tetraazaderivatives (four donor nitrogen atoms), ligands and corresponding complexes in accordance with the present invention can be prepared from the following:

N, N '

In addition, using only one organic polymacrocycle, preferably a cross-bridged cyclamide derivative, a wide variety of bleach catalysts of the present invention can be prepared; many are believed to be new compounds. Preferred transition metal catalysts, both cyclamic or cross-bridged non-cyclamic derivatives, are illustrated by the following structures (not an exhaustive list):

^c « ^h -nC1 ci \ I. Me cF I X '

PF ₆ - ^N U

hb ₆ In further embodiments of the invention are complexes of transition metals, such as Mn, Fe or Cr complexes, especially in the oxidation state of the complex (II) and / or (III), wherein

Wherein R ¹ is independently selected from H (preferably not H) and linear or branched, substituted or unsubstituted C 1 -C 20 alkyl, alkenyl or alkynyl, and L is any linker disclosed herein, eg, 1.9 or 1.10;

wherein R ¹ is as defined above; m, n, o, and p can vary independently and are integers that can be zero or positive integers and can be changed independently, provided that the sum of m + n + o + p is from 0 to 8 and L is any of the linking groups defined above,

wherein X and Y may be any of R ¹ as defined above, m, n, o and p are as defined above, and q is an integer, preferably from 1 to 4 or more generally; · I · 4 · (CHi) m

Where N is any linking group according to the invention, X and Y may be any of R ¹ as defined above and m, n, o and p are as defined above. is another useful ligand:

wherein R ¹ is any of the R ¹ units defined above.

Pendant groups

The macropolycyclic rigid ligands and corresponding transition metal complexes and compositions of the invention may also include one or more pendant groups in addition to or in place of the R ¹ groups. These pendant groups are illustrated by the following figure (not limiting):

- (CH _{2) n} -CH ₃

- (CH ₂ ) _n - CN

- (CH ₂ ) _n -C (O) NR ₂ - (CH ₂ ) _n -C (O) OR

- (CH ₂ ) _n -C (O) NH ₂

- (CH ₂ ) _n -C (O) OH

- (CH _{2) n} -OH (CH ₂₎ NR

• · ⁿ '······ · · · · · · ··· ·· ··; Wherein R is, for example, C 1 -C 12 alkyl, more typically C 1 -C 4 alkyl and Z and T are as defined in 1.10. Pendant groups may be useful, for example, when it is desired to ensure the solubility of the catalyst in a particular co-solvent.

Alternatively, the complexes of any of the foregoing highly rigid cross-bridged macropolycyclic ligands with any of said metals are equivalent within the scope of the invention.

Preferred are catalysts wherein the transition metal is selected from manganese and ^iron: manganese is most preferred. Also preferred are catalysts wherein the mole ratio of transition metal to macropolycyclic ligand in the transition metal bleach catalyst is 1: 1 and more preferably wherein the catalyst comprises only one metal per transition metal complex. Further preferred are bleach catalysts which are monometallic mononuclear complexes. The term monometallic, mononuclear complex, as indicated, is used to denote transition metal bleach catalysts to identify and distinguish a preferred class of compounds containing only one metal atom per compound molecule and only one metal atom per mole of cross-bridged macropolycyclic ligand.

Preferred transition metal bleach catalysts are those having at least four of the donor atoms in the cross-bridged macropolycyclic ligand, preferably at least four nitrogen donor atoms, two of which form an apical binding angle with the same transition metal of 180 +/- 50 ° and two of them form at least one equatorial bond with angles of 90 +/- 20 °. These catalysts preferably have a total of four or five nitrogen donor atoms and have a coordinating geometry selected from disrupted octahedral (including trigonal antiprismatic and generally tetragonal distortion) and disrupted trigonal prismatic arrangement, and preferably one where the cross-bridged macropolycyclic ligand is in a folded conformation ( has been described, for example, in Hancock and Martell, Chem. Rev., 1989, 89, page 1894). The folded conformation of the cross-bridged macropolycyclic ligand in the transition metal complex is further illustrated below:

• ·

This catalyst is a complex of Example 1 below. The central atom is Mn, the two ligands on the right are chloride, and the B cyclamic ligand occupies the left side of the disrupted octahedral structure. The complex contains an angle of N-Mn-N of 158 ° comprising two donor atoms in axial positions, the corresponding angle of N-Mn-N for donor nitrogen atoms in the plane of the chloride ligands is 83.2 °.

In other words, the preferred laundry, detergent and cleaning compositions of the present invention comprise transition metal complexes with a macropolycyclic ligand in which the folded conformation of the mycrocycle is energetically preferred as opposed to the "open" and / or "flame" and / or "flat" conformations. By way of comparison, an unfavorable conformation is, for example, some of the transsuperstructures listed in Hancock and Martell, Chemical Reviews, (1989), 89 on page 1894 (see Figure 18), incorporated herein by reference.

In light of the just described coordination, the present invention includes bleaching compositions comprising bleach catalysts based on transition metals, in particular based on Mn (II) or Μη (ΠΙ) or optionally on Fe (II) or Fe (III) or Cr (II) or Cr (III), wherein two of the donor atoms in the macropolycyclic rigid ligand, preferably two nitrogen atoms, occupy each other trans-position in the coordinating geometry, and at least two of the donor atoms in the macropolycyclic rigid ligand, preferably at least two nitrogen atoms, occupy the cisquatorial position in coordination geometry, including such cases where there is a significant geometry failure as previously reported.

The compositions of the invention may further include transition metal bleach catalysts in which the number of asymmetric sites may vary widely; thus both absolute S- and R- configurations may be included as well as geometric isomerism. The transition metal bleach catalysts may further comprise mixtures of geometric isomers or stereoisomers.

Catalyst cleaning

In general, the purity state of a transition metal bleach catalyst may vary, provided that any impurity such as synthesis by-products, free ligands, unreacted transition metal salts, colloidal organic and inorganic particles, and the like are not present in amounts that would significantly reduce the use of a transition metal bleach catalyst. It has been found that a preferred embodiment of the present invention is one wherein the transition metal bleach catalyst is purified by any suitable method that significantly

does not consume available oxygen (AvO). Excessive AvO consumption is defined as any case of exponential loss of AvO concentration in a bleach, oxidation or catalytic solution with time at 20-40 ° C. Preferred transition metal bleach catalysts of the invention, whether purified or not, are placed in a dilute aqueous buffered alkaline solution at a pH of about 9 (carbonate / bicarbonate buffer) at temperatures of about 40 ° C and have a relatively stable reduction in the over time; in preferred cases, this reduction rate is linear or approximately linear. In preferred embodiments of the invention, the rate of AvO consumption at 40 ° C is given by the slope of the% AvO versus time (in seconds) graph (hereinafter referred to as the AvO slope) and is from about -0.0050 to about -0.0500, more preferably from -0 0100 to about -0.0200. Thus, preferred Mn (II) bleach catalysts of the invention have an AvO slope of from about -0.0140 to about -0.0182; in contrast, the slightly less preferred bleach catalysts based on transition metals have an AvO slope of -0.0286.

Preferred methods for determining AvO consumption in aqueous transition metal bleach catalyst solutions include the well known iodometric method or variants thereof, such as those commonly applied to hydrogen peroxide. See. e.g. Organic peroxides, Vol. 2, D. Swem (Ed.), Wiley-Interscience, New York, 1971, e.g., p. 585 and references therein, including P. D. Barlett and R. Altscul, J. Amer. Chem. Soc., 67, 812 (1945) and W.E. Cass, J. Amer. Chem. Soc., 68, 1976 (1946). Accelerators such as ammonium molybdate may be used. The general procedure used in this invention is to prepare an aqueous catalyst and hydrogen peroxide solution in a mildly alkaline buffer, eg carbonate / bicarbonate buffer at pH 9, and to monitor the consumption of hydrogen peroxide by periodically removing aliquots of the solution that are "retarded" before further loss of hydrogen peroxide acidification, using glacial acetic acid, preferably under ice-cooling. These aliquots can then be analyzed by reaction with potassium iodide, optionally but often preferably using ammonium molybdate (especially low impurity molybdate, see, e.g., U.S. 4,596,701) to complete the reaction, followed by back titration using sodium thiosulfate. Other variants of the analytical procedure may be used, such as thermometric methods, potential buffer methods (Ishibashi et al., Anal. Chim. Acta (1992), 261 (1-2), 405-10) or photometric methods for the determination of hydrogen peroxide ( EP 485,000 A2, May 13, 1992). Variations of methods permitting fractional determination, eg, peroxyacetic acid and hydrogen peroxide, in the presence or absence of the bleach catalyst of the invention are also useful; viz. e.g. JP 92-303215, Oct. 16, 1992.

«·» • · · · • · · · • · · · * · · « • · · · · · • · · e · · • · • · · · • · · · · • · · · ·

In another embodiment of the present invention, detergent and cleaning compositions are included comprising transition metal bleach catalysts that have been cleaned up to levels having a differential reduction in AvO loss of at least 10% compared to a catalyst-free situation (units are dimensionless because they represent a ratio between the AvO slope when reacting with a bleach catalyst based on a transition metal to the AvO slope in the absence of this catalyst (essentially the ratio between the AvO). In other words, the AvO guideline is improved by cleaning so that it falls within the above preferred ranges.

In another embodiment of the present invention, two processes have been identified that are particularly effective in adjusting the suitability of transition metal bleach catalysts for incorporation into laundry and cleaning compositions or for use as a useful oxidation catalyst.

One such process is any process comprising the step of treating a transition metal bleach catalyst prepared in a solid state by extraction with an aromatic hydrocarbon solvent; suitable solvents are oxidatively stable under the conditions used and include benzene and toluene, preferably toluene. Surprisingly, toluene extraction can measurably improve the AvO slope (see description above).

Another method that can be used to improve the AvO slope of a transition metal bleach catalyst is by filtering its solution using any filtration process to remove small or colloidal particles. These procedures include the use of a fine pore filter, centrifugation or coagulation of colloidal solids.

More specifically, the process for purifying the transition metal bleach catalyst of the present invention may include:

(a) dissolving the transition metal bleach catalyst in hot acetonitrile;

(b) filtering the resulting solution hot, e.g. at temperatures of about 70 ° C, through glass microfibers (e.g. glass microfibre filter paper, commercially available from Whatman);

(c) if desired, filtering the solution after first filtration through a 0.2 µm membrane (for example, 0.2 µm filters commercially available from Millipore) or centrifuging any colloidal particles so obtained).

(d) evaporating the solution from the second filtration to dryness; (e) washing the solid of step (d) with toluene, eg, five times using toluene in an amount that is twice the volume of the bleach catalyst solid;

(f) drying the product of step (e).

• · · ·

Another process that can be used in combination with washing and removing particles by means of extraction with an aromatic solvent is recrystallization. Recrystallization, for example, of a bleach catalyst based on the complex of Bcyclam and Mn (II) chloride, can be carried out in hot acetonitrile. Recrystallization can have its disadvantages, eg it can be expensive in some cases.

The present invention has numerous alternative embodiments and branches. E.g. in the field of laundry detergents or detergent additives, the invention may include all kinds of bleach-containing or bleach-containing compositions, including, for example, fully formulated strong granular detergent compositions containing sodium perborate or sodium percarbonate and / or preformed peroxyacid derivatives such as OXONE as the primary oxidizing agent , a transition metal catalyst of the invention and a bleach activator such as tetraacetylethylenediamine or the like, with or without a nonanoyloxybenzenesulfonate salt, and the like.

Other suitable formulations include additional laundry bleach powders, granular or tablet form dishwashing detergents and bathroom cleaners. For solid form preparations, the catalyst system may lack solvent (water) - this is added by the user along with the substrate (soiled surfaces) to be cleaned (or contains dirt to be oxidized).

Other suitable embodiments of the present invention include dentifrices or dentures. Suitable formulations to which the transition metal complex may be added include dentifrice formulations containing stabilized sodium percarbonate according to US Patent 5,476,607, which are derived from compositions comprising a compressed blend of anhydrous perborate, perborate monohydrate and lubricant, monopersulfate, ungranulated perborate monohydrate, proteolytic enzyme and complexing agent, although enzyme-free preparations are also very effective. Optionally, excipients, binders, binders, paints, fragrances, and surfactants can be added to these formulations and are added according to the intended use. RE 32,771 discloses further dentifrice compositions to which a combination of a transition metal catalyst and a bleach activator and / or an organic peroxyacid may advantageously be added. For example, by simply admixing, for example, 0.00001% to 0.1% transition metal bleach catalyst of the present invention and 0.1% to about 25% bleach activator and / or organic peroxycarboxylic acid, a cleaning composition is provided which is particularly " 9 " »Μ · ·;;;;;;;;;;;;;;;;;;;;;;;;;;;; Suitable for compression into tablets; the composition also includes phosphate salts, a modified perborate salt composition, wherein the treatment comprises a combination of anhydrous perborate and perborate monohydrate in amounts of from about 50% to 70% of the total weight of the cleaning composition, wherein the combination comprises at least 20% said combination having a portion present in the form of a compressed granular composition with 0.01% to about 0.70% by weight of said combination of a polymeric fluorocarbon and a chelating or complexing agent present in amounts greater than 10% up to about 50% by weight of the total composition, wherein said cleaning composition is capable of cleaning soiled surfaces and the like by allowing it to soak for 5 minutes or less after dissolving the composition in water and causing a significant improvement in solution purity due to higher disintegration capability and improved cleaning performance efficacy than previously known compositions. Of course, dentifrice cleaning products need not be overly sophisticated: additives that are not necessary to exhibit catalytic oxidation, such as fluorinated polymers, can be omitted from the composition if desired.

In a further, non-limiting, illustration of the present invention, the combination of a transition metal catalyst and a bleach activator and / or organic peroxyacid may be added to effervescent dentifrice compositions including monoperphthalates, e.g., magnesium salts thereof, and / or compositions according to US Patent 4,490,269 , incorporated herein by reference. Preferred dentifrice cleansers are those in tablet form wherein the tablet is characterized by an active oxygen level in the range of from 100 to about 200 mg / tablet and the compositions are characterized by a degree of odor retention of at least 50% after 6 hours or more. See. U.S. 5,486,304, incorporated herein by reference for some details, in particular regarding fragrance preservation.

Advantages of the present invention are in detergent compositions having improved bleaching properties as compared to compositions not containing a selected combination of a transition metal catalyst and a bleach activator and / or an organic peroxyacid. This improved bleaching is obtained using very low concentrations of the transition metal bleach catalyst. The invention includes embodiments which are particularly suitable for washing fabrics having a low tendency to be damaged by repeated washing. However, a number of other advantages can be provided, for example, the compositions may be relatively more aggressive as needed, e.g., for cleaning tough surfaces soiled with stubborn dirt, such as furnace interiors or kitchen surfaces that have dirt coatings that are difficult to remove. The formulations can be used in the pre-mode as well. * *: Ff- i * *: ff- i For example, when releasing dirt in the kitchen or bathroom, as well as the main wash mode, eg as a fully formulated strong detergent granules. In addition to the effects of improved bleaching and / or soil removal, other benefits of the compositions of the present invention include their effectiveness in improving the sanitary condition of surfaces ranging from washed fabrics to surfaces in kitchens or bathroom equipment. Without being bound by theory, it is believed that formulations can help control or kill a wide variety of bacteria, viruses, subviral particles and fungi, as well as disrupt inanimate proteins and / or peptides such as some toxins. .

The transition metal bleach catalysts of the present invention can be synthesized by any conventional route. Specific synthetic methods are illustrated in the following examples (not an exhaustive summary).

DETAILED DESCRIPTION OF THE INVENTION

Example 1 - Synthesis [Mn (Bcyclam) Cl2]

CK I ... N- \ .Mn)

C <I i

Vj (a) Method I

Bcyclam (5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane) was prepared by the synthetic procedure described in GR Weisman, et al., J. Amer. Chem. Soc., (1990), 112, 8604. Bycyclam (1.00 g, 3.93 mmol) was dissolved in 35 mL of dry acetonitrile (distilled from CaH ₂ ). The solution was then evacuated at 15 mm until the boiling of acetonitrile. The flask was then brought to atmospheric pressure with argon. This air removal procedure was repeated four times. Mn (pyridine) 2Cl 2 (1.12 g, 3.93 mmol), prepared according to Procedure přidán, was then added under Ar atmosphere. T. Witteveen et al., J. Inorg. Nucl. Chem., (1974), 36, 1535. The cloudy reaction solution began to darken. The mixture was stirred overnight at room temperature and the reaction solution darkened and finely suspended particles precipitated. The reaction mixture was filtered through a 0.2 µm filter. The filtrate was light yellow-brown in color. This filtrate was evaporated to dryness using a rotary evaporator. After drying overnight at 0.05 mm at room temperature, 1.35 g of solid product was obtained (90% yield). Elemental analysis:% Mn, 14.45; % C, 44.22; % H. 7.95; theoretically for [Mn (Bcyclam) Cl ₂ ], MnCl ₄ H ₃ O ₄ N ₂ Cl ₂ , MW = 380.26. Found:% Mn, 14.98; % C, 44.48; % H, 7.86; Ion Spray Mass Spectroscopy showed one major peak at 354 m / z. corresponding to [Mn (Bcyclam) (formate)] ⁺ .

(b) Method II

Freshly distilled Bcyclam (25.00 g, 0.0984 mol), prepared in the same manner as above, was dissolved in 900 mL of dry acetonitrile (distilled from CaH ₂ ). The solution was then evacuated at 15 mm until the boiling of acetonitrile. The flask was then impregnated with Ar at atmospheric pressure. This air removal procedure was repeated four times. MnCl ₂ (11.25 g, 0.0894 mol) was then added under Ar atmosphere. The cloudy reaction solution immediately became dark. After stirring the reaction mixture at reflux for 4 h, it completely darkened due to finely suspended particles. The reaction solution was filtered through a 0.2 μτη filter excluding air humidity. The filtrate was a slightly brownish-yellow color and was evaporated to dryness using a rotary evaporator. The resulting ocher solid was dried overnight at 0.05 mm at room temperature. The solid was then suspended in toluene (100 mL) and heated to reflux. The toluene was then decanted and the procedure repeated with another 100 ml of toluene. The toluene residue was removed on a rotary evaporator. After drying overnight at 0.05 mm at room temperature, 31.75 g of a light blue solid was obtained, 93.5% yield. Elemental analysis:% Mn,

14.45; % C, 44.22; % H, 7.95; % N, 14.73; % C1, 18.65; theoretically for [Mn (Bcyclam) Cl ₂ ], MnCl ₄ H ₃ O ₄ Cl ₂ , MW = 380.26. Found:% Mn, 14.69; % C, 44.69; % H, 7.99; % N, 14.78; %NO. 1,

18.90 (Karl Fischer Water Test, 0.68%). Ion Spray Mass Spectroscopy showed one major peak at 354 m / z corresponding to [Mn (Bcyclam) (formate)] ⁺ .

Example 2. Synthesis of [Mn (C ₄ -Byclam) Cl ₂ ], wherein C ₄ -Byclam = 5-n-butyl-12-methyl-1,5,8,12-tetraazabocyclo [6.6.2] hexadecane ·· ··· · ····

(a) Synthesis of C4-Bcyclam

The tetracyclic adduct I was prepared according to the literature method of H. Yamamoto and K. Maruoka, J. Amer. Chem. Soc., (1981), 103, 4194.1 (3.00 g, 13.5 mmol) was dissolved in 50 mL dry acetonitrile (distilled from CafL). 1-Iodobutane (24.84 g, 135 mmol) was then added to a stirred solution under Ar atmosphere. The solution was stirred at room temperature for 5 days. 4-Iodobutane (12.42 g, 67.5 mmol) was then added and the solution was stirred for an additional 5 days at room temperature. Under these conditions, I is fully monoalkylated with 1-iodobutane as shown by C NMR. Methyl iodide (26.5 g, 187 mmol) was then added and the solution was stirred at room temperature for an additional 5 days. The reaction mixture was filtered using a Whatman # 4 paper filter and vacuum. 6.05 g of white solid II (82%) was obtained.

¹³ C NMR (CDCl ₃ ) 16.3, 21.3, 21.6, 22.5, 25.8, 49.2, 49.4, 50.1, 51.4, 52.6, 53.9 54.1, 62.3, 63.5, 67.9, 79.1, 79.2 ppm. Electrospray Mass Spectrum (MH ⁺ / 2.147).

II (6.00 g, 11.0 mmol) was dissolved in 95% ethanol (500 mL). Sodium borohydride (11.0 g, 290 mmol) was added and the reaction mixture turned milky white. The reaction was stirred under Ar for three days. Hydrochloric acid (100 mL, conc.) Was then slowly added over 1 h. The reaction mixture was evaporated to dryness using a rotary evaporator. The white residue was dissolved in sodium hydroxide (500 mL, 1.00 N). This solution was extracted with toluene (2 x 150 mL). The toluene layers were combined and dried over sodium sulfate. After removal of the desiccant by filtration, toluene was evaporated to dryness using a rotary evaporator. The resulting oil was dried overnight at room temperature under high vacuum (0.05 mm). 2.95 colorless oil (90%) was obtained. The oil (2.10 g) was distilled using a short distillation apparatus (head temperature 115 ° C at 0.05 mm). Yield: 2.00 g. @ ¹³ C NMR (CDCl3) 14.0, 20.6, 27.2, 27.7, 30.5, 32.5, 51.2, 51.4, 54.1. 54.7, 55.1, 55.8, 56.5, 57.9, 58.0, 59.9 ppm. Mass spectrometry (MH +, 297).

(b) Synthesis [Mn (C4-Bcyclam) Cl2] • · 2 C4 C4 C4 «C4 C4 C4 C4 C4 C4 C4 C4 C4 C4 C4 ··· ································

C4-Bcyclam (2.00 g, 6.76 mmol) was mixed with 75 ml of dry acetonitrile (distilled from CaH _2). The solution was then evacuated to 15 mm until the boiling of acetonitrile. The flask was then brought to atmospheric pressure with Ar. This air removal procedure was repeated four times, and MnCl ₂ (0.81 g, 6.43 mmol) was added under Ar atmosphere. The tan reaction mixture darkened immediately. After stirring at reflux for 4 hours, the reaction mixture was dark colored due to finely suspended particles. The reaction solution was filtered through a 0.2 µm membrane filter to exclude air humidity. The filtrate was light ocher colored. The filtrate was then evaporated to dryness using a rotary evaporator. The resulting white solid was suspended in 50 mL of toluene and heated to reflux. The toluene was decanted and the procedure was repeated with another 100 ml of toluene. The remaining toluene was evaporated on a vacuum rotary evaporator. After drying overnight at 0.05 mm at room temperature, 2.4 g of a light blue solid (88%) was obtained. Ion Spray Mass Spectrometry showed one major peak at m / z 396, corresponding to [Mn (C4-Bcyclam) (formate) ^+] .

Example 3. Synthesis of [Mn (Bz-Bcyclam) Cl ₂ ], wherein Bz-Bcyclam = 5-benzyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane

(a) Synthesis of Bz-Bcyclam

The ligand was synthesized similar to the C4-Bcyclam described in Experiment 2 (a) above, except that benzyl bromide was used instead of 1-iodobutane.

C NMR (CDC1 ₃₎ 27.6, 28.4, 43.0, 52.1, 52.2, 54.4, 55.6, 65.4, 65.5, 56.9, 57.3, 57.8, 60.2, 60.3,

126.7, 128.0, 129.1, 141.0 ppm. Mass spectrometry (MH ⁺ , 331).

(b) Synthesis [Mn (Bz-Bcyclam) Cl ₂ ]

This complex was prepared analogously to [Mn (C4-Bcyclam) Cl _2] described above in Example 2 (b), except substituting Bz-Bcyclam C4 Bcyklamu instead. Ion Spray Mass Spectroscopy showed one major peak at m / z 430, corresponding to [Mn (BzBcyclam) (formate)] ⁺ .

AND

Example 4. Synthesis of [MnCg-Bcyclam] CH, wherein Cg-Bcyclam = 5-n-octyl-12-methyl-1,5,8,12-tetraazabocyclo [6.6.2] hexadecane

(a) Synthesis of Cg-Bcyclam

The ligand was synthesized similar to the C4-Bcyclam described above in Experiment 2 (a), except that 1-iodooctane was used instead of 1-iodobutane.

Mass spectrometry (MH ⁺ , 353).

(b) Synthesis [Mn (C8-Bcyclam) Cl2]

This complex was prepared similar to the [Mn (C4-Byclam) Cl2] described above in Example 2 (b), except that Cg-Byclam was used instead of C4-Byclam. Ion Spray Mass Spectroscopy showed one major peak at m / z 452, corresponding to [Mn (C8Bcyclam) (formate)] ⁺ .

Example 5. Synthesis of [Mn (H2-Bcyclam) Cl2], wherein H2-Bcyclam bicyclo [6.6.2] hexadecane

1,5,8,12-tetraazaClCl

PL-Bcyclam was synthesized similar to the C4-Bcyclam described above, except that benzyl bromide was used instead of 1-iodobutane and methyl iodide. The benzyl group was then removed by catalytic hydrogenation. The resulting 5,12-dibenzyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane was then mixed with 10% Pd on carbon and dissolved in 85% acetic acid. This solution was stirred for 3 days at room temperature under 1 atm of hydrogen. The solution was then filtered through a 0.2 µm filter using vacuum. Evaporation of the solvent gave the product as a colorless oil (90%).

· • • • • ·

9 9 · · ··· · · · · · ·

The η complex was prepared similar to the [Mn (Bcyclam) Cl2] described above in Example 1 (b), except that Fh-BCyclam was used instead of Bcyclam.

Elemental analysis:% C, 40.92; % H, 7.44; % N, 15.91; theoretically for [Mn (H 2 -cyclohex) Cl 2], MnCl ₂ H 26 N ₄ Cl 2, MW = 352.2. Found:% C, 41.00; % H, 7.60; % N, 15.80. Ion Spray Mass Spectroscopy showed one major peak at m / z 317 corresponding to [Mn (H2-Bcyclam) Cl)] ⁺ and another minor peak at 352 m / z corresponding to [Mn (H2-Bcyclam) Cl2] ⁺ .

Example 6. Synthesis of [Fe (H2-Bcyclam) Cl2] wherein EE-Bcyclam bicyclo [6.6.2] hexadecane

1,5,8,12-tetraazaCl

Cl

The Fe complex was prepared similarly to the Mn (H2-Bcyclam) Cl2 described in Example 5, except that FeCE was used instead of MnCl2. Elemental analysis:% C, 40.82; % H, 7.42; % N, 15.87; theoretically for [Fe (H ₂ -Byclam) Cl ₂ ], FeCl 3 N 4 N 2 b, MW = 353.1. Found:% C, 39.29; % H, 7.49; % N, 15.00. Ion Spray Mass Spectroscopy showed one major peak at m / z 318, corresponding to [Fe (H2-Bcyclam) Cl)] ⁺ and another minor peak at 353 m / z, corresponding to [Fe (H2BcyclamjCyT)

Example 7

Synthesis of Chloro-20-methyl-9,20,24,25-pentaazatetracyklo [7.7.7.1 ^{3 '7} .l ^11.15.] Pentakosa3,5,7 (24), 11,13,15 (25) - manganese hexaen (II) hexafluorophosphate, 7 (b);

Trifluoromethanesulfono-20-methyl-1,9,20,24,25-pentaazatetracyclo [7.7.7.1 ³ ' ^{7. 11} ' ^15. ] - Pentacose 3,5,7 (24), 11,13,15 (25) - hexaene manganese (II) trifluoromethanesulfonate, 7 (c) and thiocyanato-20-methyl-9,20,24,25-pentaazatetracyklo [7.7.7.1 ^{3 '7} .l ^11.15.] pentakosa3,5,7 (24 , 11,13,15 (2S) -hexaen iron (II) thiocyanate, 7 (d) (a) Synthesis of 20-methyl-1,9,9,20,24,25-pentaazatetracyclo [7.7.7.1 ³ ' ^7] ligand. ^11,15 .] pentacose 3,5,7 (24), 11,13,15 (25) -hexaene

The ligand 7-methyl-3,7,1 l, 17-tetraazabicyclo [1.3.1 l ^17] heptadeca-l (17), 13,15-triene was synthesized according to the literature procedure KP Balakrishnan et al., J. Chem. Soc., Dalton Trans., 1990, 2965.

7-Methyl-3,7,11,17-tetraazabicyclo [11.3.1 ^17] heptadeca-l (17), 13,15-triene (1.49 g, 6 mmol) and O, O'-bis (methanesulfonate) -2,6-pyridine dimethanol (1.77 g, 6 mmol) was separately dissolved in 60 mL acetonitrile. They were then added via a piston pump (at a rate of 1.2 ml / h) to a suspension of anhydrous sodium carbonate (53 g, 0.5 mol) in 1380 ml of acetonitrile. The reaction temperature was maintained at 65 ° C for a total reaction time of 60 h.

After cooling, the solvent was removed under reduced pressure and the residue was dissolved in sodium hydroxide solution (200 mL, 4 M). The product was then extracted with benzene (6 x 100 mL) and the combined organic layers were dried over anhydrous sodium sulfate. After filtering off the desiccant, the solvent was removed under reduced pressure. The product was then dissolved in acetonitrile / triethylamine (95: 5) and passed through a column of neutral alumina (2.5 x 12 cm). After removal of the solvent, 0.93 g of a white solid (44%) was obtained.

This product can be further purified by crystallization from ethanol / diethyl ether, which upon cooling to 0 ° C overnight gave a white crystalline solid. Analysis calculated for C 21 H 29 N 5:% C, 71.75; % H, 8.32; % N, 19.93. Found:% C, 71.41; % H, 8.00; % N, 20.00. Mass spectrometry showed expected molecular peak [for C21H29N5U at m / z = 352. 1 H NMR spectrum (400 MHz, CD ₃ CN) showed peaks at δ = 1.81 (m, 4H), 2.19 (s, 3H) 2.56 (t, 4H), 3.52 (t, 4H), 3.68 (AB, 4H), 4.13 (AB, 4H), 6.53 (d, 4H) and 7.07 ( t, 2H). ¹³ C NMR spectrum (75.6 MHz, CD ₃ CN) showed 8 signals δ = 24.05, 58.52, 60.95, 62.94,121.5, 137.44 and 159.33 ppm.

All metal complexing reactions were performed in an inert dry box atmosphere using distilled and degassed solvents.

(b) Complexation of Li ligand with bis (pyridine) manganese (II) chloride

Bis (pyridine) manganese (II) chloride was synthesized according to literature procedure Η. T. Witteveen et al., J. Inorg. Nucl. Chem., 1974, 36, 1535.

Ligand L1 (1.24 g, 3.5 mmol), triethylamine (0.35 g, 3.5 mmol) and sodium hexafluorophosphate (0.588 g, 3.5 mmol) were dissolved in 12 mL of pyridine. Then bis (pyridine) manganese (II) chloride was added and the reaction was stirred overnight. The reaction was then filtered and the solid collected. The solid was then washed with acetonitrile until the solvent was discolored and the organic filtrates were combined and evaporated under reduced pressure. The residue was dissolved in a minimum amount of acetonitrile and allowed to evaporate overnight to give reds.

Krystal ······························································································································· crystals. Yield: 0.8 g (39%). Calcd. For C25 H17 N5 N2 ClCl3 / •% C, 43.00; % H,

4.99; % N, 11.95. Found:% C, 42.88; % H, 4.80; % N, 11.86. The mass spectrum showed the expected molecular peak [for C CzHsiNNsMniClliPPFé] * for m / z 441. The electronic spectrum of the dilute solution in water showed two absorption bands at 260 and 414 nm (e - 1.47 x 10 ³ and 773 M -1 cm ^-1 ). . The IR spectrum (KBR) of the complex showed a band at 1600 cm ^-1 (pyridine) and a strong band at 840 and 558 cm ^-1 (PF ₆ ·).

(c) Ligand complexation with manganese (Π) trifluoromethanesulfonate

Manganese (II) trifluoromethanesulfonate was prepared according to the literature procedure of Bryan and Dabrowiak, Inorg. Chem., 1975, 14,297.

Manganese (II) trifluoromethanesulfonate (0.883 g, 2.5 mmol) was dissolved in 5 mL acetonitrile and this solution was added to a solution of ligands L 1 (0.878 g, 2.5 mmol) and triethylamine (0.25 g, 2.5 mmol). ) in 5 ml acetonitrile. The mixture was then heated for 2 h, filtered and after cooling the solvent was removed under reduced pressure. The residue was dissolved in a minimum amount of acetonitrile and allowed to slowly evaporate to give orange crystals. Yield 1.06 g (60%).

Analysis calculated for MniC23H29N5S2F6O _6:% C, 39.20; % H, 4.15; % N, 9.95. Found:% C,

38.83; % H, 4.35; % N, 10.10. Mass spectrometry showed the expected molecular peak [for Mn ^ ^ NsSiFsOsf at m / z = 555. The electronic spectrum of the diluted aqueous solution of the complex showed absorption bands at 260 and 412 nm (ε = 9733 and 607 M ^ cm ^-1 ). The IR spectrum (KBr) of the complex showed a band for 1600 cm ^-1 (pyridine) and 1260, 1160 and 1030 cm ^-1 (CF 3 SO 3).

(d) Complexation of ligands with ferric trifluoromethanesulfonate

Ferrous trifluoromethanesulfonate was prepared according to the literature procedure of Tait and Busch,

Inorg. Synth., 1978, XVIII, 7.

The ligand (0.833 g, 2.5 mmol) and triethylamine (0.505 g, 5 mmol) were dissolved in 5 mL acetonitrile. To this solution was added a solution of iron (II) hexakis (acetonitrile) trifluoromethanesulfonate (1.5 g, 2.5 mmol) in 5 mL acetonitrile to give a dark red solution. Sodium thiocyanate (0.406 g, 5 mmol) was then added and the reaction mixture was further stirred for 1 h. The solvent was removed under reduced pressure and the resulting solid was recrystallized from methanol to give red microcrystals. Yield 0.65 g (50%). Analysis calculated for FEICO 2H29N _{7 2} S _2:% C, 52.76; % H, 5.59; % N, 18.74. Found:% C, 52.96; % H, 5.53; % N, 18.55.

Mass spectrometry showed the expected molecular peak [for FeiC22H29NoSi] ⁺ at m / z = 465. ¹ H NMR (300 MHz, CD ₃ CN) δ = 1.70 (AB, 2H), 2.0 (AB, 2H), 2.24 (s, 3H), 2.39 (m, 2H), 2.70 (m, 4H), 3.68 (m, 4H), 3.95 (m, 4H), 4.2 (AB) 2H), 7.09 (d, 2H), 7.19 (d, 2H), 7.52 (t, 1H), 7.61

(d, 1 H). The IR spectrum (KBr) showed a peak at 1608 cm ^-1 (pyridine) and strong peaks at 2099 and 2037 cm ^-1 (SCN ').

Bleach activators and organic percarboxylic acids

Another essential component of the compositions and methods of this invention are bleach activators, organic percarboxylic acids, or mixtures thereof. Organic peroxyacids include, for example, hydrophilic and hydrophobic mono- and di-peroxyacids. These may be percarboxylic acids, peroxyimidic acids, amidoperoxycarboxylic acids or salts thereof including calcium, magnesium or mixed salts. Peroxy acids of various kinds can be used both in free form and as precursors, known as bleach activators, which, when combined with a source of hydrogen peroxide, liberate the corresponding peroxyacids by perhydrolysis.

Organic peroxycarboxylic acids useful as oxygen bleach activators include magnesium monoperoxyphthalate hexahydrate, available from Interox, m-chloroperoxybenzoic acid and salts thereof, 4-nonylamino-4-oxoperoxybutyric acid, and diperoxydodecanedioic acid and salts thereof. These bleaches are described in U.S. Pat. No. 4,483,781, U.S. Pat. Appl. 740,446, Bums et al., Filed Jun. 3, 1985, EP-A 133,354, published Feb. 20, 1985, and U. S. 4,412,934. Highly preferred oxygen bleaches also include those having the formula HO-OC (O) -RY, wherein R is an alkylene or substituted alkylene group containing from 1 to about 22 carbon atoms or a phenylene group or substituted phenylene group and Y is hydrogen, halogen, alkyl, aryl or -C (O) -OH or -C (O) -O-OH.

Organic percarboxylic acids useful herein include those containing one, two, or more peroxy groups and may be aliphatic or aromatic. When the organic peroxyacid is aliphatic, the unsubstituted acid has a suitable linear formula: HO-OC (O) - (CH ₂ ) _n -Y, where Y may be eg H, CH ₃ , CH ₂ Cl, COOH or C (O) OOH; and n is an integer from 1 to 20. Branched analogues are also acceptable. When the organic peroxyacid is aromatic, the unsubstituted acid has the appropriate formula: OH-OC (O) -C ₆ H ₄ -Y, wherein Y is hydrogen, alkyl, alkylhylogen, halogen, or -COOH or -C (O) OOH.

Monoperoxycarboxylic acids useful as oxygen bleaches are further illustrated by alkyl percarboxylic acids and aryl percarboxylic acids such as peroxybenzoic acid and ring-substituted peroxybenzoic acids such as peroxyalpha-naphthoic acid; substituted aliphatic and arylalkyl monoperoxyacids such as peroxylauric acid, peroxystearic acid and N, N-phthaloylaminoperoxycaproic acid (PAP) and 6-octylamino-6-oxoperoxyhexanoic acid. The monoperoxycarboxylic acids may be hydrophilic, such as peracetic acid, or may be relatively hydrophobic. The hydrophobic type includes those containing a chain of six or more atoms, preferred hydrophobic types having a linear C8-Cu aliphatic chain which is optionally substituted with one or more ether-oxygen atoms and / or one or more aromatic groups positioned such that the peroxyacid is an aliphatic peroxyacid . More generally, this optional substitution with an ether oxygen atom and / or aromatic groups may be applied to any peroxyacid or bleach activator of the invention. Branched-chain peroxyacids and aromatic peroxyacids having one or more C 3 -C 16 linear or branched long chains as substituents may also be useful. The peroxyacids can be used in the form of acids or any suitable salt with any bleach-stable cation. Very useful are organic peroxycarboxylic acids of the formula:

θ O O, II ~ II π ||

R1-CN-R2-C-00H _; R1 NC> R2-C-OOH R5 p5 or mixtures thereof, wherein R ¹ is alkyl, aryl, or alkaryl containing from about 1 to about 14 carbon atoms, R is an alkylene, arylene or alkarylene containing from about 1 to about 14 carbon atoms and R ⁵ is H, aryl or alkaryl containing from 1 to about 10 carbon atoms. If these acids have a combined carbon atom in R and R together of 6 or more, preferably from 8 to about 14, they are particularly suitable as hydrophobic peroxyacids for bleaching a variety of relatively hydrophobic or lipophilic spots, including the so-called faded type. Calcium, magnesium or substituted ammonium salts may also be useful.

Other useful peroxyacids and bleach activators of the invention are from the family of imidoperoxyacids and imido bleach activators. These include phthaloylimidoperoxycaproic acid and the corresponding arylimidosubstituted and acyloxy nitrogen derivatives. For a list of such substances, their preparations and uses see. US 5,487,818, US 5,470,988, US 5,466,825, US 5,419,846, US 5,416,796, US 5,391,324, US 5,328,634, US 5,310,934, US 5,279,757, US 5,246,620, US 5,246,620, US 5,246,620, US 5,246,620, US 5,246,620, US 5,246,620 S. 5,087,385.

Useful diperoxy acids include, for example, 1,12-diperoxydodecanedioic acid (DPDA), 1,9-diperoxyazelaic acid, dieperoxybrasilic acid, diperoxysebacic acid and diperoxyisophthalic acid, 2-decyldiperoxybutane-1,4-dioic acid and 4,4 '· · · · · sulfonylbisperoxybenzoic acid. Because of the structures in which two relatively hydrophilic groups are exposed at the end of the molecule, diperoxy acids are sometimes classified separately from hydrophilic and hydrophobic monoperoxy acids, eg, as a hydrotrope. Some of these diperoxy acids are hydrophobic in the true sense, especially if they have a long chain separating peroxyacid groups.

More generally, the terms hydrophilic and hydrophobic as used herein in connection with oxygen bleaches, in particular peroxyacids and bleach activators, are based on the first approximation of whether the oxygen bleach effectively bleaches transient colors in solution, thereby preventing graying and discoloration of the fabric, and / or removes more hydrophilic stains such as tea, wine, grape juice - in which case it is called hydrophilic. If the oxygen bleaching agent or bleach activator has a significant stain removal effect, it improves the whiteness or cleansing effect on faded dirt, fat, carotenoids, or other hydrophobic contamination, it is called hydrophobic. The term can also be applied to peroxyacids or bleach activators used in combination with hydrogen peroxide sources. The current comparative offer of hydrophilic oxygen bleach systems is: TAED or proxyacetic acid comparing hydrophilic bleach. NOBS or NAPAA are the corresponding comparators for hydrophilic bleaching. The terms hydrophilic, hydrophobic and hydrotropic with reference to oxygen bleaches including peroxyacids and herein extended to bleach activators have also been used in the literature in a somewhat narrower sense. See. Othme Encyclopedia of Chemical Technology, Vol. 4., pp. 284-285. This reference includes chromatographic retention times and critical micelle concentrations upon which the criteria are based and is therefore useful for identifying and / or characterizing preferred subclasses of hydrophobic, hydrophilic and hydrotropic oxygen bleach activators that can be used in the present invention.

Bleach activators useful in the present invention include amides, imides, esters and anhydrides. Usually there is at least one substituted or unsubstituted acyl group covalently bonded to a leaving group such as in the structure R-C (O) -L, wherein R is a C 2 -C 18 saturated or unsaturated alkyl, aryl or arylalkyl group. In one preferred use, the bleach activators are combined with a hydrogen peroxide source, such as perborates or peroxycarbonates, in a single product. Usually, a single product leads to the in situ formation of peroxycarboxylic acid in aqueous solution (i.e. during the washing process) which corresponds to the respective bleach activator. The product itself may contain water, such as a powder, provided that the amount of water and its mobility are controlled, so that storage stability is: · · · · · · · · ··,. ··········· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · Alternatively, the product may be an anhydrous solid or liquid. In another embodiment of the present invention, the bleach activator or oxygen bleach is introduced by means of a pre-acting product, such as a bar-shaped composition, to rub the dirty spot, and the pre-treated substrate may then be subjected to further processing, e.g. In view of the above structure of the bleach activator RC (O) L, the atom in the leaving group is attached to the acyl group RC (O) - from which the peroxyacid is formed, most commonly O or N. Bleach activators can have uncharged, positively or negatively charged groups to form peroxyacid and / or uncharged, positively or negatively charged leaving groups. One or more peroxyacid groups or leaving groups may be present. See. e.g., U.S. Patent 5,595,967, U.S. Patent 5,561,235, U.S. Patent 5,560,862 or the bis (peroxycarbon) system in U.S. Patent 5,534,179. The bleach activators may be substituted with electrononomy or electronceptine groups, either in the leaving group or in the peroxyacid group, or in groups that alter their reactivity and make them more or less suitable for a particular pH or wash condition. E.g. electron acceptance groups such as NO2 improve the efficacy of bleach activators intended for use at low pH (e.g., pH around 7.5 to 9.5).

Cationic bleach activators include quaternary carbamates, quaternary carbonates, quaternary esters, and quaternary amides, thereby providing a variety of cationic peroxyimidic, peroxycarboxylic and peroxycarboxylic acids for washing. An analogous, but not cationic, bleach activator range is available when quaternary derivatives are not required. Cationic activators include quaternary ammonium substituted activators which are described in more detail in WO 96-06915, US 4,751,015 and 4,397,757, EP-A-284,292, EP-A-331,229 and EP-A03520 include 2- (N, N, N-trimethylammonium) ) ethyl 4-sulfophenyl carbonate (SPCC), N-octyl-N, N-dimethyl-N-10-carbophenoxydecylammonium chloride (ODC), 3-N, N, N-trimethylammonium) propyl sodium 4-sulfophenylcarboxylate and Ν, Ν, Ν -trimethylammoniumtoluyloxybenzenesulfonate. Also useful are cationic nitriles as described in EP-A-303,520 and European Patent Specifications 458,396 and 464,880. Other types of nitriles have electron acceptance groups as described in U. S. 5,591,378, examples include 3,5-dimethoxybenzonitrile and 3,5-dinitrobenzonitrile.

Further descriptions of bleach activators include GB 836,988, 864,798, 907,356, 1,003,310 and 1,519,351, German patents 3,337,921, EP-A-0185522, EP-A-0174132, EP-A-0120591, U. S.

Pat. 1,246,339, 3,332,882, 4,128,494, 4,412,934 and 4,675,393 and the phenol sulfonate esters of the alkanoylamino acids described in U. S. 5,523,434. Suitable bleach activators include any acetylated diamines, whether hydrophilic or hydrophobic in nature.

Of the above bleach precursors, preferred classes include esters, including acylphenolsulfonates, acylalkylphenolsulfonates or acyloxybenzenesulfonates (OBS leaving group), acylamides and quaternary ammonium substituted peroxyacid precursors, including cationic nitriles.

Preferred hydrophilic bleach activators include Ν, Ν, Ν ', Ν'-tetraacetylethylenediamine (TEDA) or any related substances including triacetyl or other asymmetric derivatives. TAED and acetylated sugars such as glucose pentaacetate and xylose tetraacetate are preferred hydrophilic bleach activators. Depending on the application, the acetyltriethyl citrate liquid as well as the phenylbenzoate also have utility.

Preferred hydrophobic bleach activators include sodium nonanoyloxybenzene sulfonate (NOBS or SNOBS), lauryloxybenzene sulfonate and decanoyloxybenzoic acid or salts thereof, substituted amides, described in more detail below, such as NAPAA-derived activators and activators derived from certain imidoperacetic bleaches, e.g. On October 29, 1991 and assigned to the Hoechst Aktiengesellschaft, Frankfurt, Germany. Japanese laid-open patent application (Kokai) 4-28799, for example, discloses bleaching agents and bleaching detergent compositions including organic peroxyacid precursors described by the formula and illustrated by compounds that may be summarized more precisely as compounds of the following formula:

Wherein L is sodium p-phenol sulfonate, R is CH 3 or C 12 H 25 and R is H. Also useful are analogs of these compounds having any leaving group described herein and / or having R ¹ linear or branched C 6 -C 16.

Another class of peroxyacids and bleach activators of the present invention are those forms of derivatives that are derived from imidoperoxycarboxylic acids and their salts of the general formula:

· · · · · · · · · · · · · · · · · · · · · · · · · · · · O ·

if

E — c

Ν — X — C — OO) M q ⁺

EC (i) ⁰ ;

cyclic imidoperoxycarboxylic acids and their salts of general formula

O

II from ^C with (A Ν X X C 0 O) M q + (ii) and (iii) a mixture of said compounds, (i) and (ii), wherein M is selected from hydrogen and bleaching compatible cations having a charge q ; and y and z are integers such that said compound is electrically neutral; E, A and X include hydrocarbon groups and said terminal hydrocarbon groups are contained in E and A. The structure of the corresponding bleach activators is obtained by erasing the peroxy group and the metal and replacing it with a leaving group L, which may be any leaving group defined in of the invention. In a preferred embodiment of the invention there is provided a detergent composition wherein in any of said compounds X is a linear C 3 -C 8 alkyl; And is selected from:

Rl r3

Rl

R2-

wherein n is from 0 to about 4 and

Rl

R3

wherein R ¹ and E are said terminal hydrocarbon groups, R ² , R ³ and R ⁴ are independently selected from H, C 1 -C 3 saturated alkyl and C 1 -C 3 unsaturated alkyl, and wherein said terminal hydrocarbon radicals are alkyl groups comprising at least six carbon atoms atoms, more typically linear or branched alkyls having from about 8 to about 16 carbon atoms.

• · * ·

Other suitable bleach activators include sodium 4-benzyloxybenzenesulfonate (SBOBS), sodium 1-methyl-2-benzyloxybenzenesulfonate, sodium 4-methyl-3-benzyloxybenzoate (SPCC), trimethylammonium toluyloxybenzenesulfonate or sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate.

Bleach activators are used in any amount, typically up to 20%, preferably from 0.1 to 10% by weight of the composition, although larger amounts of 40% or more are useful, e.g., in highly concentrated bleach supplementary forms or those intended for automatic dosing.

Highly preferred bleach activators useful in this invention are substituted amides of formula:

9 ⁰⁰ , II _n II II ||

CNR.2 _{Rl-L-C-R-L-C N} R2 C L or a mixture thereof, wherein R ¹ is alkyl, aryl, or alkaryl containing from about 1 to about 14 carbon atoms including both hydrophilic types ( short R ¹ ) as well as hydrophobic types (R ¹ is especially from 6, preferably from 8 to about 12), R ² is alkylene, arylene or alkarylene containing from 1 to about 14 carbon atoms, R ⁵ is H or alkyl, aryl or alkaryl containing from 1 to about 10 carbon atoms and L is a leaving group.

A leaving group as defined herein is any group that is replaced in the bleach activator as a result of attack with a perhydroxide or equivalent agent capable of releasing a stronger bleach in the reaction. Thus, the bleach activator perhydrolyses to form the free peroxyacid. The leaving groups for the bleach activators for the relatively low pH of the washing solutions are preferably electronceptual. Preferred leaving groups have low rates of back association with the group from which they have been displaced. The leaving groups of bleach activators are preferably selected such that their removal and peroxyacid formation are rate consistent with the desired application, e.g., a wash cycle. In practice, the equilibrium is disrupted in that the leaving group is not adequately released and the activator is not adequately hydrolyzed or perhydrolyzed while being stored in the bleaching composition. The pK of the conjugated acid is a measure of convenience and is typically from about 4 to about 16 or greater, preferably from 6 to about 12, more preferably from 8 to 11.

• • •

Preferred bleach activators include those having, for example, the above substituted amide formula and wherein R ¹ , R ² and R ³ are defined for the corresponding peroxyacid and L is selected from the group consisting of:

R ³ γ

I |

O-CH-C-CH-CH ₂ -O-CH = C-CH = CH ₂

O

-OC-R ¹

O

II ch ₂ -c / \

II o

R ³ —O — C = CHR ⁴ , and —N — s — CH — R ⁴ I, II R ³ O

and mixtures thereof, wherein R ¹ is a linear or branched alkyl, aryl or alkaryl group containing from o

to about 14 carbon atoms, R is an alkyl chain containing from 1 to about 8 carbon atoms, R ⁴ is H or R ^3, and Y is H or a dissolution facilitating group. These and other known leaving groups are generally suitable alternatives for introduction into any of the bleach activators of the present invention. Preferred solubility enhancing groups include -SC 1 M ', -CChM / SO fM 1 -N * (R) 4X' and O-N (R ³ ) 2, more preferably -SC 1 FM and -CO ₂ * M ⁺ , where R ³ is an alkyl chain containing from 1 to about 4 carbon atoms, M is a bleach-stable cation and X is a bleach-stable anion, each selected in accordance with the desired solubility of the activator. Under certain conditions, eg solid European very strong granular detergents is preferably any of the above solid bleach activators having a crystalline character and a melting point above 50 ° C. In these cases, it is preferred that the branched alkyl groups are not included in the oxygen bleach or activator with the bleach. In another context, e.g., strong bleaching liquids or bleaching additives, liquid bleach activators are preferred. The lowering of the melting point may be favored by the introduction of branched alkyl radicals into the oxygen bleach or precursor thereof, rather than the introduction of linear alkyl groups.

When soluble groups are added to the leaving group, the activator may obtain good water solubility or dispersibility, although it is still capable of providing a relatively hydrophobic proxy acid. Preferably, M is an alkali metal, ammonium or substituted ammonium ion, more preferably Na or K, and X is a halide, hydroxide, methyl sulfate or acetate. Soluble groups may more generally be used in any of the bleach activators described herein. Bleach activators of low solubility, e.g., those that do not have a solubility promoting group in the leaving group, can be finely dispersed or dispersed in the bleaching solution to obtain acceptable results.

Preferred bleach activators also include those of the above formulas in which L is selected from the group consisting of:

R3

R 3 Y wherein R ³ is as defined above and Y is -SO3 M ⁺ or ^_ _-CO2 -M ⁺ wherein M is as defined above. Preferred examples of bleach activators of the above formulas include: (6-octanamido-caproyl) oxybenzenesulfonate, (6-nonanamido-caproyl) oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzenesulfonate, and mixtures thereof.

Other useful activators described in U.S. Pat. No. 4,966,723 are of the benzoxazine type, such as the C 11 L ring, to which the C (O) OC (R)) = N- group is fused at position 1,2.

Depending on the activator and the particular application, good whitening effects can be obtained with whitening systems having a pH in use of from 6 to about 13, preferably from 9.0 to about 10.5. Typically, activators with electron accepting groups for near neutral or subneutral pH are used, for example. Alkalis and buffer systems can be used to provide such pH.

Acyllactam activators are very useful according to the invention, especially acylcaprolactams (see e.g. WO 94-28102 A) and acylvalerolactams (see U. S. 5,503,639) of the formula:

wherein R ⁶ is H, alkyl, aryl, alkoxyaryl, alkaryl having from 1 to about 12 carbon atoms, or substituted phenyl having from 6 to about 18 carbon atoms. See. also US 4,545,784 which discloses acyl caprolactams, including benzoyl caprolactam absorbed on sodium perborate. In some preferred embodiments of the present invention, NOBS, lactam activators, imide activators or amidfunctionalized activators, especially those more hydrophobic derivatives, are suitably combined with hydrophilic activators such as TAED, typically in a hydrophobic activator: TAED weight ratio ranging from 1: 5 to 5: 1 , preferably about 1: 1. Other suitable lactam activators are alpha modified. WO 96-22350 A1, July 25, 1996. Lactam activators, particularly more hydrophobic types, are suitably used in combination with TAED, typically in a weight ratio of amide derivative or caprolactam activator: TAED in the range of 1: 5 to 5: 1, preferably around 1 - 1. See also bleach activators having a cyclic amidine leaving group described in US 5,552,556.

Unlimited examples of other activators useful in the present invention can be found in U.

Nos. 4,915,854, U. S. 4,412,934 and 4,634,551. Hydrophobic activators nonanoyloxybenzenesulfonate (NOBS) and hydrophilic tetraacetylethylenediamine (TAED) are typical, and mixtures thereof may also be used.

· · / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / · · ··· · · ··· · · · ·

The excellent whitening and cleansing effect of the compositions of the present invention is also advantageously achieved by their safety to parts of apparatus made of natural rubber, eg in some European washing machines (see WO 94-28104) and other natural rubber products, including textiles containing natural rubber and elastic materials with natural rubber. The complexity of the bleaching mechanisms is great and is not yet fully understood.

Other activators useful in the present invention include those described in U. S. 5,545,349.

Examples include esters of organic acid and ethylene glycol, diethylene glycol or glycerin, or imides of organic acids and ethylenediamine, wherein the organic acid is selected from methoxyacetic acid, 2-methoxypropionic acid, p-methoxybenzoic acid, ethoxyacetic acid, 2-ethoxypropionic acid, p-ethoxybenzoic acid , propoxyacetic acid, 2-propoxypropionic acid, p-propoxybenzoic acid, butoxyacetic acid, 2-butoxypropionic acid, p-butyloxybenzoic acid, 2methoxyethoxyacetic acid, 2-methoxy-1-methylethoxyacetic acid, 2-methoxy-2methylethoxyacetic acid, 2-ethoxyacetic acid 2- (2-ethoxyethoxy) propionic acid, p- (2-ethoxyethoxy) benzoic acid, 2-ethoxy-1-methylethoxyacetic acid, 2ethoxy-2-methylethoxyacetic acid, 2-propoxyethoxyacetic acid, 2-propoxy-1-methylethoxyacetic acid, 2 -propoxy-2-methylethoxyacetic acid, 2-butoxyethoxyacetic acid, 2-butoxy-1-methylethoxy acetic acid, 2-butoxy-2-methylethoxyacetic acid, 2- (2-methoxyethoxy) ethoxyacetic acid, 2- (2-methoxy-1-methylethoxy) ethoxyacetic acid, 2- (2-methoxy-2-methylethoxy) ethoxyacetic acid and 2 - (2-ethoxyethoxy) ethoxyacetic acid.

Oxygen bleaching agents

Preferred compositions of the invention include, as part or all of the washing or cleaning material, oxygen bleaching agents. The oxygen bleaching agents useful in the present invention may be any of the oxidizing agents known in laundering, hard surface cleaning, automatic dishwashing, or dental restoration other than the basic organic peroxyacids previously described. Oxygen bleaching agents or mixtures thereof are preferred, although other oxidizing agents such as hydrogen peroxide producing systems may also be used.

Oxygen bleaches (including organic peroxycarboxylic acids) provide available oxygen (AvO) or active oxygen, which is typically measurable by standard methods such as iodide / thiosulfate titration or cerium sulfate. See. the well-known work of Swem or the Kirk Othme Encyclopedia of Chemical Technology under the heading of bleaching agents. When the bleaching agent is a peroxy compound, it comprises an -O-O- linkage with a single O that is active in each such linkage. The content of AvO in such bleaching agents is usually expressed as a percentage and is equal to 100 times the number of active oxygen atoms x (16 / molecular weight of the oxygen bleaching compound).

The process for combining catalyst, bleach activator and / or organic peroxycarboxylic acid and oxygen bleach may vary. For example, the catalyst, bleach activator and / or organic peroxyacid and oxygen bleach may be incorporated into a single product or may be used in various combinations of pre-use products in the form of dirt bars, main laundry products and even post-laundry products such as fabric conditioners or products added to dry linen. The oxygen bleach may be in any physical form compatible with the intended application, more particularly liquid and solid forms of the thigh oxygen bleaches as additives, promoters or activators are included. Liquids may be contained in solid detergents, eg, absorbed on an inert carrier, and solids may be contained in liquid detergents, eg using suitable suspending agents.

Common oxygen species of the peroxygen type include hydrogen peroxide, inorganic peroxyhydrates and organic peroxohydrates.

According to the present invention, inorganic peroxides such as Na ₂ O ₂ , superoxides such as KO ₂ , organic hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide and inorganic peroxyacids and their salts such as peroxosulfuric acid salts, especially sodium peroxodisulfate acids and more preferably peroxomonosulphuric acids, including the commercial triple salt sold under the name OXONE by DuPont, as well as any commercially available equivalent such as CUROX from Azko or CAROAT from Degussa. Some organic peroxides, such as dibenzoyl peroxide, may be particularly useful as additives rather than as primary oxygen bleaches.

Mixed oxygen bleach systems are generally useful in the present invention as they are mixtures of any oxygen bleaching agent with a known bleach activator, organic catalysts, enzymatic catalysts, and mixtures thereof. In addition, such compositions may further include brighteners, photo-bleaches, and color transfer inhibitors of all types known in the art.

Preferred oxygen bleaches, as already mentioned, include peroxohydrates, sometimes known as perhydrates or perhydrates. These are organic or more often inorganic salts, capable of releasing hydrogen peroxide readily. They include those in which hydrogen peroxide is present as a true crystal hydrate and those in which hydrogen peroxide is incorporated covalently and is released chemically, eg by hydrolysis. Typically, peroxyhydrates provide hydrogen peroxide sufficiently easily that it can be extracted in measurable amounts into the ether phase in an ether / water mixture. Peroxohydrates are characterized in that they do not give a Reisenfeld reaction, unlike some of the other oxygen bleaches described below. Peroxohydrates are the most common examples of hydrogen peroxide sources and include perborates, percarbonates, perfosphates, and persilicates. Other materials that serve to produce or release hydrogen peroxide are of course also useful. Mixtures of two or more peroxohydrates may also be used, eg, where different solubility is desired. Suitable peroxohydrates include sodium carbonate peroxyhydrate and the equivalent of commercial percarbonate bleaches and any of the so-called sodium perborate hydrates, with tetraborate and monohydrate being preferred, although sodium pyrophosphate peroxyhydrate may also be used. Many of these peroxohydrates are available in a prepared coated form such as silicate and / or borate and / or waxy material and / or surfactants or have particles of a certain geometry, such as compact spheres, which improve storage stability. Urea peroxyhydrate may also be useful herein as organic peroxyhydrates.

For example, the percarbonate bleach comprises dry particles having a diameter in the range of 500 microns to about 1000 microns, wherein no more than about 10% by weight of the particles is less than about 200 microns and no more than about 10% by weight of the particles is greater than about 1250 microns. . Percarbonates and perborates are widely commercially available, e.g., from FMC, Solvay and Tokai Denka.

Enzymatic sources of hydrogen peroxide

On the principle other than the oxygen bleaching agents described above, suitable hydrogen peroxide generating systems are based on a combination of a C 1 -C 4 alkanol oxidase and C 1 -C 4 alcohols, especially a combination of methanol oxidase (MOX) and ethanol. These combinations are described in WO 94/03003. Other bleach-related enzymatic materials can also be used in the compositions of the present invention, such as peroxidases, haloperoxidases, oxidases, superoxide dismutases, catalase and enhancers thereof, or more commonly inhibitors.

• fc ··

Oxygen transfer agents and precursors

Any oxygen transfer agent or precursor thereof is also useful in the present invention. These include the compounds themselves and / or their precursors, e.g., any suitable ketone for the production of dioxiranes and / or any heteroanalogens of dioxirane precursors or dioxiranes, such as sulfonimines R * R ² C = NSO ² R ³ ; EP 446 982 A, published 1991 and sulfonyloxaziridines such as:

X ° r1r2c — N — SO2R3 see. EP 446,981 A, published 1991. Preferred examples of these materials include hydrophilic or hydrophobic ketones, used in particular in combination with monoperoxysulfates to produce the in situ dioxirans and / or imines described in U.S. Patent 5,576,282 and references therein. Oxygen bleaching agents preferably used in conjunction with these oxygen transfer agents or precursors thereof include peroxycarboxylic acids and salts, peroxycarboxylic acids and salts, peroxymonosulfuric acid and salts, and mixtures thereof. See also U. S. 5,360,568, U.S. Pat. 5,360,569 and U. S. 5,370,826. In a highly preferred embodiment, the invention relates to detergent compositions comprising a transition metal bleach catalyst according to the invention and an organic bleach catalyst such as one of the above and at least one other detergent, hard surface cleaner or automatic dishwashing additive. Among these formulations, those that include a precursor for a hydrophobic oxygen bleach such as NOBS are preferred.

Although oxygen bleaching systems and / or precursors thereof may be susceptible to decomposition during storage in the presence of moisture, air (oxygen and / or carbon dioxide) and metal traces (especially rust or simple salts or colloidal transition metal oxides) or when exposed to light , stability can be improved by adding a conventional complexing agent (chelant) and / or a polymeric dispersing agent and / or a small amount of an antioxidant to the bleaching system or product. See. eg, U. S. 5,545,349. Antioxidants are often added to detergent ingredients ranging from enzymes to surfactants. Their presence is not necessarily inconsistent with the use of oxidizing bleaches, eg the established phase barriers can be used to stabilize a putative incompatible combination of enzyme and antioxidant on the one hand and oxidative bleach on the other. Although commonly known compounds can be used as antioxidants, those preferred include phenol-based antioxidants such as 3,5-di-tert-butyl-4-hydroxytoluene and 2,5-di-tert-butylhydroquinone, amine-based antioxidants such as N, N'75 * Diphenyl-p-phenylenediamine and phenyl-4-piperazinyl carbonate, sulfur-based antioxidants such as didodecyl-3,3'-thiodipropionate and ditridecyl-3,3'-thiodipropionate, phosphorus-based antioxidants such as tris (isodecyl) phosphate and triphenyl phosphate and natural antioxidants such as L-ascorbic acid, its sodium salt and DL-alpha-tocopherol. These oxidants may be used independently or in combination of two or more. Of the above, 2,5-di-tert-butylhydroquinone and DLalpha-tocopherol are particularly preferred. When used, the antioxidants are blended into the bleaching composition of the present invention preferably in the range of 0.01 to 1.0% by weight of the organic peracid precursor, and particularly preferably in the range of 0.05 to 0.5% by weight. The hydrogen peroxide or peroxide produced by the hydrogen peroxide in the aqueous solution is admixed to the mixture during use preferably in the range from 0.5 to 98% (w / w) and particularly preferably in the range from 1 to 50% so that the effective oxygen concentration is preferably from 0.1 to 3% (w / w) and particularly preferably from 0.2 to 2% (w / w). In addition, the organic peroxyacid precursor is admixed to the formulation during use in the range of 0.1 to 50% (w / w) and particularly preferably in the range of 0.5 to 30% (w / w). Without being bound by theory, antioxidants work by inhibiting or quenching free radicals, which may be particularly beneficial in suppressing the destruction of fabrics.

The combination of the components used with the transition metal bleach catalyst according to the present invention can be varied widely, some particularly preferred embodiments of the present invention are those which include: one or more detersive surfactants, especially including medium chain branched anionic types having excellent solubility at low temperatures such as medium chain branched alkyl sulfates, although the use of nonionic detersive surfactants is also very useful, especially in compact forms of strong granular detergent compositions; polymeric dispersants, especially including biodegradable hydrophobically modified and / or terpolymeric types; complexing agents such as certain penta (methylene phosphonates) or ethylenediamine disuccinates; fluorescent whitening agents; enzymes, including those capable of generating hydrogen peroxide; photobleaches and / or color transfer inhibitors. Conventional binders, buffers or alkalis and combinations of various purification-promoting enzymes, in particular protease, cellulase, keratinase and / or lipase, may also be added. In these combinations, the transition metal bleach catalysts will preferably be at concentrations suitable to provide a wash (usable) concentration of from 0.1 to about 10 ppm (catalyst weight), the other components will typically be used at known concentrations that may be widely used. be different.

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While there is currently no particular advantage, the transition metal bleach catalysts of the present invention can be used in combination with the various transition metal bleaches described or color transfer inhibiting catalysts such as Mn and Fe triazacyclononane complexes, Fe N, N- complexes bis (pyridin-2-ylmethyl) bis (pyridin-2yl) methylamine (US 5,580,485) and the like. For example, if the transition metal bleach catalyst is one that is particularly effective for solution bleaching and color transfer inhibition, as is the case with some transition metal porphyrins, they may be combined with a single catalyst more suitable for accelerating the interphase bleaching of dirty substrates.

Washing and cleaning consumables and applications

In general, the laundry or cleaning additive materials are any materials required to convert a composition comprising a transition metal bleach catalyst and a bleach activator and / or an organic peroxyacid into a composition useful for washing or cleaning purposes. The addition generally includes stabilizers, diluents, a structure supporting the materials, and materials having an independent or dependent cleaning function. In preferred embodiments of the present invention, laundry or cleaning additives are recognizable to those of skill in the art as they are absolutely characteristic of laundry and cleaning products, especially laundry and cleaning products intended for direct use by consumers in the home environment.

Although not essential for the purposes of the present invention as most commonly defined, some of these conventional additives described below may be suitable for incorporation into preferred embodiments of the present invention, eg, to assist or enhance the cleaning effect, to treat a cleaned substrate, or to modifying the appearance of the detergent composition as is the case with perfumes, colorants, colors, and the like. The exact nature of these additives and the level of their concentration will depend on the physical form of the formulation and the nature of the cleaning operation for which they are intended.

Unless otherwise indicated, the detergents or detergent additive compositions of the invention may, for example, be formulated as granules or as strong laundry powder forms for all uses, especially laundry detergents; liquids, gels or paste forms of general purpose laundry detergents, especially so-called strong liquid types; liquid detergents for delicate fabrics; hand wash agents or weak dishwashing agents, in particular of the high sudsing type; automatic dishwashing agents, including various tablets, granules, liquids and rinsing agents for domestic or institutional use; liquid cleaning and disinfecting agents, including • antibacterial agents for washing hands, laundry sticks, mouthwashes, dentifrices, car or bath foams, and metal cleaners, as well as various other cleaners such as bleaching additives and dirt bars or pre-use agents.

The additives should preferably have good stability with the bleaches used in the present invention. Some preferred detergent compositions of the present invention should be boron-free and phosphate-free. Preferred car wash compositions may contain non-chlorine and chlorine bleaching agents. Typical additive concentrations are from 30% to about 99.9%, preferably from 70% to about 95% by weight of the composition.

Typical additives include binders, surfactants, enzymes, polymers and the like. with the exception of any of the materials defined above as part of the basic ingredients of the compositions of the invention. Other additives may include various active ingredients or specialized materials such as dispersing polymers (eg, from BASF Corp. or Rohm & Haas), colored dots, silver care materials, anti-turbidity or anti-corrosion agents, paints, fillers, germicides , sources of alkaline materials, hydrotropes, antioxidants, enzyme stabilizing agents, perfumes, dissolution enhancing agents, carriers, excipients, pigments and, for liquid formulations, solvents as described below.

Typically, the laundry and cleaning compositions of the present invention such as laundry detergents, laundry detergent additives, hard surface particles, automatic dishwashing detergents, fabric softeners and fabric treatment fluids, solids and items of all kinds will require several additives, although some simply formulated products, such as bleaching additives, may require only a metal catalyst and bleach activator and / or organic peracid and one additional material, such as a detergent or surfactant binder, to help create an effective catalyst available to the consumer in a form that can work .

Detersive surfactants

The compositions of the invention suitably include detersive surfactants. Detersive surfactants are widely described in U. S. 3,929,678, December 30, 1975 (Laughlin et al.) And U. S. 4,259,217, March 31, 1981 (Murphy); in the series Surfactant Science, Marcel Dekker, Inc., New York and Basel; in Handbook of Surfactants, M.R. Porter, Chapman and Hall, 2nd edition 1994; in Surfactants in Consumer Products, Ed. J. Falbe, Spring-Verlag, 1987, and in numerous detergent patents assigned to Procter & Gamble and patents of other detergent and consumer product manufacturers.

The detersive surfactants of the present invention are generally at least partially water-soluble surfactant materials that form micelles and have a cleaning function, more specifically assist in removing fat from fabrics and / or suspend dirt removed from the fabric during the laundry process, although some detersive surfactants are useful for more specialized uses such as cosurfactants to assist in the primary cleaning process of another surfactant component, or as wetting or hydrotropic agents, as viscosity modifiers, as coating agents, as binders, as fabric softeners, or as suds suppressors.

The detersive surfactants of the invention include at least one amphiphilic compound, i.e., a compound having a hydrophobic tail and a hydrophilic head that forms a foam in water. Foam testing is known in the literature and generally includes a test by shaking or mechanically stirring a solution or dispersion of a detersive surfactant in distilled water at a concentration, temperature and mixing conditions that are designed to model the conditions intended for fabric washing. Such conditions include concentrations in the range of about 10 @ ^-6 mol / 1 to about 10⁻⁴ mole / 1 and the temperature from 5 ° C to 90 ° C. Foam testing devices are described in the aforementioned patents and the Surfactant Series, e.g., vol. 45.

Thus, the detersive surfactants of the present invention include anionic, nonionic, zwitterionic or amphoteric types of surfactants known for use as laundry detergents, but do not include completely non-foaming surfactants or completely insoluble surfactants (although these may be used as an optional additive). Examples of types of surfactants that are considered optional for the purposes of the present invention are relatively unusual compared to cleansing surfactants, but include, for example, conventional fabric softening materials such as dioctadecyldimethylammonium chloride.

In particular, detersive surfactants for use in the present invention are typically at concentrations from 1% to 55% by weight and preferably include: (1) alkylbenzene sulfonates including linear or branched types, (2) olefin sulfonates including α-olefin sulfonates and fatty acid and ester derived sulfonates (3) alkyl or alkenyl sulfosuccinates including diester and half ester types as well as sulfosuccinamates and other sulfonate / carboxylate surfactant types such as sulfosuccinates derived from ethoxylated alcohols and alkanolamides; , including the products of bisulfite addition to alpha olefins, (5) alkyl naphthalenesulfonates, (6) alkyl isethionates and alkoxypropanesulfonates, as well as fatty isethionate esters, fatty esters of ethoxylated isethionates, and other ester sulfonates such as the 3-hydroxypropanesulfo ester (7) benzene, cumene, toluene, xylene and naphthalene sulfonates, (8) alkyl ether sulfonates, (9) alkylamide sulfonates, (10) α-sulfofatty acid salts or their esters and internal esters of sulfofatty acids, (11) alkylglycerylsulfonates , (12) lignin sulphonates, (13) petroelum sulphonates, sometimes known as heavy alkyl sulphonates, (14) diphenyloxide disulphonates, (15) alkyl sulphates or alkenyl sulphates, (16) alkyl or alkylphenolalkoxylated sulphates and corresponding polyalkoxylates, sometimes known as alkyl ether sulphates, as well as alkyl ether sulphates or alkenyl polyalkoxy sulphates, (17) alkylamide sulphates or alkenylamide sulphates, including sulphated alkanolamides and their alkoxylates and polyalkoxylates, (18) sulphated oils, sulphated alkyl glycerides, sulphated alkyl polyglycosides or sulphated sugar-derived surfactants, ) alkyl esters (21) alkyl or alkenyl amide alkoxy and polyalkoxy carboxylates; , aminopropionates and iminopropionates, (24) amide soaps, sometimes referred to as fatty acid cyanamides, (25) alkylpolyaminocarboxylates, (26) phosphorus-based surfactants, including alkyl or alkenyl phosphate esters, alkyl ether phosphates, including their alkoxylated derivatives, salts of alkyl phosphate acids, alkyl phosphate salts , alkyl di (polyoxyalkylene alkanol) phosphates, amphoteric phosphates such as lecithins and phosphate / carboxylase, phosphate / sulfate and phosphate / sulfonate types, (27) non-ionic Pluronic and Tetronic type surfactants, (28) so-called EO / BO block polymers, including diblock types and triblocks (29) bridged and non-bridged alkyl or alkylphenol ethoxylates, propoxylates and butoxylates, including polyethylene glycol esters of fatty alcohols, (31) fatty alcohols, especially where they are useful as viscosity modifying surfactants or where they are present as (32) N-alkyl polyhydroxy fatty acid amides, in particular alkyl-N-alkyl glucamides, (33) non-ionic surfactants derived from mono- or polysaccharides or sorbitan, especially alkyl polyglycosides, as well as sucrose fatty acid esters, (34) ethylene glycol-, propylene glycol, glycerol and polyglycerol esters and their alkoxylates, in particular glycerol ethers and, in particular, glycerol ethers;

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Monoesters and diesters of glycerin with fatty acids, (35) aldobionamide surfactants, (36) alkyl succinimide type nonionic surfactants, (37) acetylenic alcoholic surfactants such as SURFYNOL, (38) alkanolamide surfactants and their alkoxylated derivatives, including alkanolamides of fatty acids and alkanolamides of fatty acids and polyglycol ethers, (39) alkylpyrrolidones, (40) alkylamine oxides, including alkoxylated or polyalkoxylated amine oxides and sugar-derived amine oxides, (41) alkylphosphmoxides, (42) sulfoxide surfactants (43) amphoteric sulfonates, especially sulfobetaines, (44) amphoteric betaine-type substances, including those derived from aminocarboxylates, (45) amphoteric sulfates such as alkylammonium polyethoxysulfates, (46) fatty alkylamines and alkylamines derived from petroleum and amine salts, (47) alkylimidazoles, (48) alkylamidoamines and their alkoxylates and polyalkoxylate derivatives, (49) conventions the cationic surfactants, including water-soluble alkyl trimethylammonium salts. In addition, less common types of surfactants are included, such as: (50) alkylamidoamine oxides, carboxylates and quaternary salts, (51) sugar-derived surfactants, other than any of the aforementioned non-specific types, (52) fluorosurfactants, (53) biosurfactants, (54) ) organosilicon surfactants, (55) geminisurfactants, other than the aforementioned diphenyloxide disulfonates, including glucose derivatives, (56) polymeric surfactants, including amphopolycarboxyglycinates, and (57) bolform surfactants.

For any of the above surfactants, the hydrophobic chain typically has a length in the range of C 5 to C 20, with a length of C 5 to C 16 being preferred, especially when the wash is to be performed in cold water. The choice of chain length and degree of alkoxylation for conventional purposes is described in standard texts. If the detersive surfactant is a salt, any compatible cation, including H (i.e., the acidic or partially acidic form of a potentially acidic surfactant), Na, K, Mg, ammonium or alkanolammonium, or a combination of cations, may be present. Normally, mixtures of detersive surfactants having different charges are preferred, especially anionic / nonionic, anionic / nonionic / cationic, anionic / nonionic / amphoteric, nonionic / cationic and nonionic / amphoteric mixtures. In addition, any detersive surfactant can be replaced, often due to the desired cold water wash effect, by mixtures of otherwise similar detersive surfactants having different chain lengths, degree of unsaturation or branching, degree of alkoxylation (especially ethoxylation), introduction of substituents such as ether oxygen atoms in hydrophobes or any combination thereof.

Among the above-mentioned surfactants are preferred: the acidic, sodium and ammonium salts of C9 to C20 alkyl benzene sulfonates, especially sodium benzene sulfonates with linear secondary C10.

to C15 benzenesulfonates (1), including straight-chain or branched forms, olefin sulphonate salts (2), i.e. a material formed by the reaction of olefins, especially C10 to C20Ot olefins with sulfur trioxide and then neutralization and hydrolysis of the reaction product, sodium and ammonium C7 to C12 dialkyl sulfosuccinates (3), alkanmonosulfonates (4), such as those formed by the reaction of C8 to C20 aolefins with sodium bisulfite and those formed by the reaction of paraffins with SO2 and CI2 and then hydrolysis with a base to form random sulfonates, salts or esters of α- sulfo fatty acids (10), sodium alkyl glyceryl sulfonates (11), in particular tallow or coconut oil higher alcohol ethers and synthetic alcohols derived from petroleum, alkyl or alkenyl sulfates (15), which may be primary or secondary, saturated or unsaturated, branched or unbranched. These compounds, when branched, may be branched randomly or periodically. If they are secondary, they preferably have the formula CH ₃ (CH 2) x (CHOSO ₃ 'M ⁺ ) CH 3 or CH 2 Cl 2 / CHOSO 5 M + jCIECHs, where x and (y + 1) are integers greater than or equal to 7, preferably at least 9 and M is a water-soluble cation, preferably sodium. When unsaturated, sulphates such as oleyl sulphate are preferred, while sodium or ammonium alkyl sulphates, especially those produced by the sulphation of C 5 to C 18 alcohols, e.g. from tallow or coconut oil, are also useful, alkyl or alkenyl ether sulphates are also preferred ( 16), in particular ethoxysulphates having about 0.5 moles or more ethoxylation, preferably from 0.5 to 8 moles, alkyl ether carboxylates (19), in particular EO 1-5 ethoxycarboxylates, soaps or fatty acids (21), preferably types more water-soluble, amino acid types of surfactants (23) such as sarcosinates, especially oleyl sarcosinate, phosphate esters (26), alkyl or alkylphenol ethoxylates, propoxylates and butoxylates (30), especially AE ethoxylates, including the so-called narrow fraction of alkyl ethoxylates and C 6 -C 12 alkylphenolalkoxylates as well as products of aliphatic primary or secondary linear or branched alcohols with ethylene oxide, generally S-30 EO, N-alkyl polyhydroxy fatty acid amides, especially C12 to C18 N-methylglucamides (32), cf. WO 9206154 and amides of Nalkoxypolyhydroxy fatty acids such as C10 to N- (3-methoxypropyl) glucamide, while N-propyl to N-hexyl C12 to C18 glucamides can be used for lower foaming, alkylpolyglycosides (33), amine oxides (40), especially alkyldimethylamine N-oxides and their dihydrates, sulfobetaines or sultenes (43), betaines (44) and geminisurfactants.

Suitable concentrations of the anionic detersive surfactants of the present invention range from about 3% to about 30% or greater, preferably from about 8% to about 20%, even more preferably from about 9% to about 18% by weight of the detergent composition.

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Suitable concentrations of the nonionic detersive surfactants of the invention are from about 1% to about 20%, preferably from about 3% to about 18%, more preferably from 5% to about 15% (w / w).

Suitable weight ratios of anionic: nonionic surfactant in combination include ratios from 1.0: 9.0 to 1.0: 0.25, preferably from 1.0: 1.5 to 1.0: 0.4.

Suitable concentrations of the cationic detersive surfactant of the invention are in the range of from 0.1% to about 10%, preferably from about 1% to about 3.5%, although higher concentrations, e.g. up to 20% or more, may be particularly useful. in nonionic: cationic (i.e., no anionic) surfactant formulations.

When present, zwitterionic detersive surfactants are generally at concentrations ranging from 0.1% to about 20% by weight of the detergent composition. Often, concentrations are limited to about 5% or less, especially when the amphoteric surfactant is expensive.

Enzymes

Enzymes are preferably included in the detergent compositions of the present invention for a variety of uses, including removing dirt based on proteins, sugars or triglycerides from various substrates, preventing unwanted dye transfer during fabric washing, and restoring fabric appearance. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof of any origin, such as vegetable, animal, bacterial, fungal or yeast origin. Preferred selection is influenced by factors such as pH activity and / or optimal stability, thermostability to the active detergent. , binders and the like. In this regard, bacterial or fungal enzymes such as bacterial amylase or fungal cellulases are preferred.

Detersive enzyme as used herein refers to any enzyme having cleaning, dirt-removing or other positive effects when washing laundry, cleaning hard surfaces or for personal care products. Preferred detersive enzymes are hydrolases, amylases and lipases. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases, and peroxidases. Amylases and / or proteases are highly preferred for automatic dishwashing, including both commercially available and treated types, which, although more and more compatible due to successful treatments, have to some extent the ability to deactivate bleaching.

The enzymes are normally incorporated into the detergent or detergent adjuncts in concentrations that guarantee an effective amount for cleaning. The term refers to any amount of substance capable of producing the effect of cleaning, removing dirt and contamination, whitening, odor removal, or enhancing the fresh appearance of substrates such as fabrics, dishes, and the like. In a practical case for commercial use, typical amounts for cleaning are in the range of about 5 mg by weight, more typically from 0.01 mg to 3 mg of active enzyme per gram of detergent composition. In other words, the compositions of the invention will typically contain from 0.001% to 5%, preferably 0.01% to 1% by weight of a commercial enzyme preparation. Protease enzymes are usually present in commercial preparations at concentrations sufficient to provide 0.005 to 0.1 Anson units (AU) of activity per gram of preparation. For some detergents, such as for automatic dishwashing, it may be desirable to increase the active enzyme content of the commercial preparation to minimize the total amount of catalyzed inactive material and thereby improve the tendency to stain or coat the final product. Higher active concentrations may also be desirable for highly concentrated detergent compositions.

Suitable examples of proteases are substilisins which are obtained from some strains of B. subtilis and B. licheniformis. One suitable protease derived from the Bacillus strain has a maximum activity in the pH range of 8-12, sold under the name ESPERASE®, and obtained by Novo® Industries A / S from Denmark, hereinafter referred to as Novo. The preparation of this and analogous enzymes is described in GB 1,243,784 (Novo). Other suitable proteases include ALCALASE® and SAVINASE® from Novo and MAXATASE® from International Bio-Synthetics, Inc., The Netherlands, as well as Protase A described in EP 130,756 A, Jan. 9, 1985 and Protease B described in EP 303,761 A, On April 28, 1987 and EP 130,756 A, on January 9, 1985. See, e.g. also a high pH protease from Bacillus NCIMB 40338, described in WO 9318140 A (Novo). Enzymatic detergents including proteases, one or more other enzymes, and a reversible protease inhibitor are described in WO 9203529 A (Novo). Other preferred proteases include those described in WO 9510591 A (Procter & Gamble). If desired, proteases having reduced adsorption and increased hydrolysis as described in WO 9507791 (Procter & Gamble) are obtainable. A recombinant trypsin-like protease suitable for the detergents of the invention is described in WO 9425583 (Novo).

More particularly, a particularly preferred protease, referred to as Protease D, is a carbonyl hydrolase variant having an amino acid sequence that is not found in nature and that is derived from a precursor carbonyl hydrolase by substituting several amino acid residues for others at position +76 of said carbonyl hydrolase, preferably also in combination with one or more exchanged amino acid residues whose positions are equivalent to positions selected from the group consisting of:. +99, +101, +103, +104, +107, +123, +27, +105, +109, +128, +128, +135, +156, +166, +195, +197, +204 , +206, +210, +216, +217, +218, +222, +260, +265 and / or +274 according to Bacillus amyloliquefaciens substillisin numbering as described in WO 95/10615, April 20, 1995 ( Genencor International).

Useful proteases are also described in PCT publications: WO 95/30010, published November 9, 1995 (Procter & Gamble), WO 95/30011, published November 9, 1995 (Procter & Gamble), WO 95/29979, published November 9, 1995 1995 (Procter & Gamble).

Amylases suitable for use in the present invention, particularly for the purpose of automatic dishwashing (but not limited to) include, for example: α-amylase described in GB 1,296,839 (Novo), RAPIDASE®, International Bio-Synthetics, Inc. and TERMAMY1® (Novo). FUNGAMYL® from Novo is particularly useful. It is known to engineer enzymes in order to improve the stability of e.g. oxidation. See. e.g., J. Biological Chem., Vol. 260, No. 11, June 11, 1985, pp. 6518-6521. Certain preferred embodiments of the compositions of the present invention may utilize amylases having improved detergent stability, such as automatic dishwashing types, specially modified oxidation stability, as measured against a reference point formed by TERMAMYL® that has been commercially used since These preferred amylases have a common characteristic - they are increasingly stable amylases, characterized by at least a minimal measurable increase in one or more of the following: oxidative stability, e.g., to hydrogen peroxidase / tetraacetylethylenediamine in a buffered solution at pH 9-10; at a conventional wash temperature such as 60 ° C or alkaline stability, e.g. at a pH of from about 8 to about 11, measured against the aforementioned reference amylase. Stability can be measured using any of the described test methods. See. e.g., the references described in WO 9402597. Amylase with enhanced stability can be obtained from Novo or Genencor International. One class of highly preferred amylases of the invention has in common that they have been derived by site-directed mutagenesis from one or more Bacillus amylases, particularly Bacillus α-amylases, regardless of whether the immediate precursor was one, two or more amylase strains. Amylases with increased oxidative stability are preferred in use over the above reference amylase, especially in bleaching, more preferably oxygen bleaching (as opposed to chlorine bleaching) compositions of the present invention. These preferred amylases include (a) the amylase of the aforementioned WO 9402597, Nov. 3, 1994, as further illustrated by a mutant in which the methionine residue at position 197 of the B. licheniformis alpha-amylase was replaced with alanine or threonine, preferably threonine, known as TERMAMYL® or a homologous position variation in a similar parent amylase such as B. amyloliquefaciens, B. subtilis or B. stearothermophilus; (b) Amylases with enhanced stability as described in Genecor International Oxidatively Resistant Alpha-Amylases, presented at the 207th National Meeting of the American Chemical Society, March 13-17, 1994 (C. Mitchinson). It has been mentioned therein that bleaches in automatic dishwashing detergents inactivate alpha-amylases, but not this modified amylase with increased oxidative stability, manufactured by Genecor of B. licheniformis NCIB8061. Methionine (Met) was found to be the most likely residue from the modification. Methionine was modified, one at each step, at positions 8, 15, 197, 256, 304, 366 and 438, resulting in specific mutations. Of particular importance is the variant M197L and M197T, with the variant M197T being the most stable variant. Stability was measured in CASCADE® and SUNLIGHT®; (c) particularly preferred amylases of the invention include amylases having further modifications in the immediate precursor as described in WO 9510603 A (Novo). It is available from this company under the name DURAMYL®. Other particularly preferred amylases with enhanced oxidative stability include those described in WO 9418314 (Genencor International) and WO 9402597 (Novo). Any amylase with increased oxidative stability can be used, such as amylases obtained by specifically targeted mutagenesis of known chimeric, hybrid or simple mutant parent forms of available amylases. Other preferred enzyme modifications are available. WO 9509909A (Novo).

Other amylase enzymes include those described in WO 95/26397 and in co-pending application of Novo Nordisk PCT / DK96 / 00056. Particular amylase enzymes for use in the detergent compositions of the present invention include α-amylases characterized by a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature of from 25 ° C to 55 ° C and at pH values of 8 to 10, measured by Phadebas® activity assay with amylase. (This Phadebas® amylase assay is described on pages 9-10, WO 95/26397). Also included are α-amylases that are at least 80% homologous to the amino acid sequence of the SEQ ED list in the reference. These enzymes are preferably incorporated into the laundry detergent compositions at concentrations from 0.00018% to 0.060% pure enzyme per total weight of the composition, more preferably from 0.00024% to 0.048% pure enzyme based on the total weight of the composition.

Celluloses suitable for use in the present invention include both bacterial and fungal types, preferably having a pH optimum between 5 and 9.5. U.S. Patent 4,435,307, March 6, 1984 (Barbesgoard et al.) Discloses suitable fungal cellulases from Humicola insolens or Humicola strain DSM1800 or a cellulose sponge 212 belonging to the genus Aeromonas and cellulases extracted from the hepatopancreas of Dolabella Auricula Solander. Suitable cellulases are also disclosed in GB-A-2,075,028, GB-A-2,095,275 and DE-OS-2,247,832. CAREZYME® and CELLUZYME® (Novo) are particularly useful. also WO 9117243.

Suitable lipase enzymes for use in detergents according to the invention include, for example, enzymes produced by Pseudomonas family microorganisms, such as Pseudomonas stutzeri ATCC 19.154 as described in GB 1,372,034. See. also lipases in Japanese Patent Application 53,20487, issued February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the tradename Lipase P Amano or Amano-P. Other suitable commercial lipases include Amano-CES, Chromobacter viscosum lipases, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U. S. Biochemical Corp., USA and Disoynth Co., The Netherlands, and lipases from Pseudomonas gladioli. LIPOLASE®, an enzyme derived from Humicola lanuginosa and available from Novo, see p. also EP 341,947, is a preferred lipase for use in the present invention. Lipases and amylase variants stabilized against peroxidase enzymes are described in WO 944951 A (Novo). See. also WO 9205249 and RD 94359044.

Despite the large number of publications devoted to lipase enzymes, only lipase derived from Humicola languinosa and produced in Aspergillus oryzae as a guest has found widespread use as an additive for laundry laundry products. It is available from Novo Nordisk under the trademark Lipolase ™ as previously mentioned. To optimize dirt removal efficiency, Novo Nordisk has made a number of variants. As described in WO 92/05249, the D96L variant of the natural lipase Humicola lanuginosa improves grease stain removal by a factor of 4.4 over the wild type lipase (enzymes were compared in amounts ranging from 0.075 to 2.5 mg per liter). Research Disclosure No. 35944, published March 10, 1994 (Novo Nordisk), discloses that the D96L lipase variant may be added in an amount corresponding to 0.001 to 100 mg (5-500,000 LU / L) of the lipase variant per liter of wash solution. The present invention provides an improvement by increasing the bleaching effect on the fabric using a low concentration of D96L variant

OJ, The detergent composition comprising a branched medium-chain long-chain surfactant as described herein, especially when the D96L variant is used at concentrations ranging from about 50 LU to 50 LU. approximately 8500 LU per liter of wash solution.

Cutinase enzymes suitable for use in the present invention are described in WO 8809367 A (Genecor).

Peroxidase enzymes can be used in combination with an oxygen source, such as percarbonate, perborate, hydrogen peroxide, etc. to bleach in solution or to prevent color transfer from a substrate during laundering to another substrate present in the wash solution. Known peroxidases include radish peroxidase, ligninase, and haloperoxidase such as chloro- or bromoperoxidase. Peroxidase formulations are described in WO 89099813 A, Oct. 19, 1989 (Novo) and WO 8909813 A (Novo).

A variety of enzymatic material and compositions for incorporation into synthetic detergent compositions are also described in WO 9307263 A and WO 9307260 A (Genencor International), WO 8908694 A (Novo) and U.S. 3,553,139, Jan. 5, 1971 (McCarty et al.). Enzymes are further described in U.S. Patent 4,101,457, June 18, 1978 (Plače et al.) And U.S. Patent 4,507,219, March 26, 1985 (Hughes). An enzyme material useful in liquid detergent formulations and its incorporation into these compositions is described in U. S. 4,261,868, April 14, 1981 (Hora et al.). Enzymes for use in detergents can be stabilized by various techniques. Techniques for stabilizing enzymes are described and exemplified in U.S. Patent 3,600,319, Aug. 17, 1971 (Gedge et al.), EP 199,405 and EP 200,586, Oct. 29, 1986 (Venegas). Enzyme stabilization systems are also described in U. S. 3,519,570. Useful species Bacillus sp. AC13 giving proteases, xylanases and cellulases is described in WO 9401532 A (Novo).

Enzyme stabilization systems

The enzyme-containing compositions of the invention may optionally also contain from 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from 0.01% to about 6% by weight of the enzyme stabilizing system. The enzyme stabilizing system may be any stabilizing system which is compatible with the other active ingredients of the composition or which may be added separately, eg by the manufacturer of detergents already containing the enzyme. Such stabilizing systems may, for example, include calcium ions, boric acid, propylene glycol, short chain carboxylic acid, boronic acids and mixtures thereof, and are designed to meet various stabilization problems depending on the type and physical form of the detergent composition.

One approach to stabilization is the use of water-soluble sources of calcium and / or magnesium ions in the final composition to provide these ions for the enzymes. Calcium ions are generated more efficiently than magnesium ions and are preferred herein when only one type of cation is used. Typical detergent compositions, especially liquids, will contain from 1 to about 30, preferably from 2 to about 20, more preferably from 8 to about 12 millimoles of calcium ions per liter of the final detergent composition, although variations may be possible depending on factors including frequency, type and concentration of incorporated enzymes. Preferably, water-soluble calcium or magnesium salts are used, including, for example, calcium chloride, calcium maleate, calcium hydroxide, and calcium acetate, more generally calcium sulfate or magnesium salt corresponding to the aforementioned examples of calcium salts may be used. Of course, further increased concentrations of calcium or magnesium may be useful, eg, to aid in the removal of greasy impurities with some types of surfactants.

Another approach to stabilizing enzymes is the use of borate particles. See. Severson, U. S. 4,537,706. Boron-based stabilizers, if used, may be in concentrations up to 10% or more by weight of the formulation, although concentrations up to 3% by weight of boric acid or other borate compounds such as borax or orthoborate are also typically used, which are also suitable for use. in liquid detergents. Substituted boric acids such as phenylboronic acid, butaneboronic acid, p-bromophenylboronic acid and the like. can be used instead of boric acid and a reduced total boron concentration in the detergent composition is possible due to the use of such substituted boron derivatives.

Stabilization systems of some detergent compositions, such as automatic dishwashing compositions, may further comprise from 0 to about 10%, preferably from 0.01% to about 6%, by weight of the chlorine bleach feeders that are added to provide chlorine bleaches potentially occurring in many water sources prevent attack and inactivation of enzymes, especially under alkaline conditions. While the concentration of chlorine in the water may be small, typically in the range of from 0.5 ppm to about 1.75 ppm, the available chlorine in the total amount of water coming into contact with the enzymes, eg during dish cleaning or laundry washing, may be relatively large, so stabilizing enzymes is sometimes a problem. Since perborate or percarbonate having the ability to react with chlorine bleach may be present in some formulations in amounts justified by a separate stabilizing system, the use of an additional chlorine stabilizer may not generally be required, although better results are obtained with its use. Suitable chlorine anions are well known and readily available and, when used, can be salts containing ammonium cations with sulfite, disulfite, thiosulfite, thiosulfate, iodide and the like. Antioxidants such as carbamates, ascorbates and the like, organic amines such as ethylenediaminetetraacetic acid (EDTA) or its alkali metals, monomethanolamine (MEA) and mixtures thereof may be used similarly. Similarly, special enzyme inhibition systems may be incorporated so that different enzymes have different maximum compatibility. Other conventional chlorine devourers such as bisulfate, nitrate, chloride, hydrogen peroxide sources such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartar, salicylate and under. and mixtures thereof may be used if desired. In general, since the function of chlorine-eating agents can be performed by components separately listed under better recognized functions (eg, hydrogen peroxide sources), there is no absolute requirement to add special chlorine-eating agents unless the compound fulfilling this function is missing to the desired degree in the enzyme containing embodiment of the present invention, even then the chlorine consumer is added only to achieve an optimum result. In addition, the formulator has established conventional chemical knowledge that prevents him from using any enzyme ingestor or stabilizer that is generally incompatible with other reactive ingredients. With regard to the use of ammonium salts, such salts may simply be mixed with the detergent composition, but are susceptible to water absorption and / or ammonia release during storage. Thus, if present, these materials should be protected in particulate form, as described in U.S. Patent 4,652,392.

Binders

Detergent binders selected from aluminosilicates and silicates are preferably included in the compositions of the invention, eg, to assist in controlling the mineral (especially Ca and / or Mg) water hardness or to assist in removing dirt particles from the surface. Alternatively, some formulations may be formulated with fully water-soluble binders, while organic or inorganic binders will depend on the intended use.

Suitable silicate binders include water-soluble and hydrated types of solids and include those having a linear, layered, or three-dimensional structure as well as amorphous solid silicates or other types, eg, specially adapted for use in unstructured liquid formulations. Preferred are alkali silicates, especially such liquids and solids having a SiO ₂ : Na ₂ O ratio ranging from 1.6: 1 to 3.2: 1, including solid hydrated silicates with a ratio of 2, especially for the purpose of automatic dishwashing, Sold by PQ Corp.. under the trade name BRITESIL®, such as BRITESIL H20, and layered silicates, such as those described in US 4,664,839, May 12, 1987, (HP Rieck). NaSKS-6, sometimes abbreviated as SKS-6, is a crystalline layered silicon-free silicate of 6-Na2SiO5 morphology, sold by Hoechst, and is particularly preferred in granular laundry laundry compositions. See. the comparative methods in German DE-A3.417,649 and DE-A-3,742,043. Other layered silicates, such as those having the general formula NaMSixChx + ryfEO, wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0, may be optionally used according to the invention. Hoechst layered silicates also include NaSKS-5, NaSKS-7 and NaSKS-11, such as α, β, and γ forms of layered silicate. Other forms of silicates may also be useful, such as magnesium silicates, which may serve as brittle granules, as bleach stabilizers, and as components of the suds control system.

Synthetic crystalline ion-exchange materials or hydrates thereof having a chain structure and formulations represented by the following general formula in anhydrous form are also suitable for use in the present invention: xMjO-γSiCUzMO, where M is Na and / or K, M 'is Ca and / or Mg , y / x is 0.5 to 2.0 and z / x is 0.005 to 1.0 as described in US 5,427,711, June 27, 1995, to Sakaguchi et al.

Aluminosilicate binders are particularly suitable for granular detergents, but may also be incorporated into liquids, pastes or gels. Suitable for use in the present invention are those having the empirical formula: [M _z (A102) _z (SiO 2) _in pxH 2 O, where zav are integers of at least 6, the molar ratio between zav is between 1.0 and 0.5 and x is an integer from 15 to 264. The aluminosilicates may be crystalline or amorphous, naturally occurring or synthetically derived. Methods for preparing aluminosilicates are described in US 3,985,669, Oct. 12, 1976 (Krummel et al.). Preferred synthetic crystalline aluminosilicate ion exchange materials are available as Zeolite A, Zeolite P (B), Zeolite X and so-called Zeolite MAP, which differ to some extent from Zeolite P. Natural types, including clinoptilolite, can also be used. Zeolite A has the formula: Na 12 [(AlO 2) 12 (SiO 2) 12] xH 2 O, where x is from 20 to 30, especially 27. Dehydrated zeolites (x = 0 to 10) can also be used. Preferably, the aluminosilicates have a particle diameter of from 0.1 to 10 µm.

Additional detergent binders may be included in the compositions of the present invention instead of or together with the silicates and aluminosilicates described above, eg, to assist in controlling mineral (especially Ca and / or Mg) hardness in the wash water or to assist in removal. Dirt particles from surfaces. Binders can act by a variety of mechanisms including forming soluble or insoluble complexes with hard ions, an ion exchange mechanism, and by providing a better surface for precipitation of hard ions than the surface of the article being cleaned. The binder concentration may vary considerably depending on the end use and physical form of the composition. Binder detergents typically contain at least about 1% binder. Liquid compositions typically comprise about 5% to 50%, more preferably 5% to 35% binder. Granular formulations typically contain from about 10% to about 80%, more preferably from 15% to about 50%, binder by weight of the detergent composition. Lower or higher binder concentrations are not excluded. For example, some detergent additives or higher surfactant compositions may be completely binder free.

Suitable binders according to the invention may be selected from the group comprising phosphates and polyphosphates, in particular sodium salts, carbonates, bicarbonates, sesquicarbonates and carbonate materials other than sodium carbonate or sesquicarbonate, organic mono-, di-, tri- and tetracarboxylates, especially water-soluble non-surfactant carboxylates in acid, sodium, potassium or alkanolammonium form, as well as oligomeric or water-soluble low molecular weight carboxylate polymers, including aliphatic and aromatic types, and folic acid. These may be supplemented with borates, eg, for pH buffering purposes, or sulfates, especially sodium sulfate and any other filler or carrier that may be important for making a stable detergent composition containing a surfactant and / or binder.

Binder mixtures, sometimes referred to as binder systems, may also be used and typically contain two or more commercial binders, optionally supplemented with chelants, pH buffers or fillers, although these additional materials are generally considered separately when describing the quantities of each material. In terms of surfactant and binder in detergent compositions of the present invention, preferred binder systems are formulated for a surfactant to binder ratio of from about 60: 1 to about 1:80. Some preferred laundry detergents have said ratio ranging from 0.90: 1.0 to 4.1: 1.0, more preferably from 0.95: 1.0 to 3.0: 1.0.

Phosphorus-containing detergent binders are often preferred where permitted by legislation, and include, but are not limited to, alkali, ammonium, and alkanolammonium salts of polyphosphates such as tripolyphosphates, pyrophosphates, glass polymer metaphosphates, and phosphonates.

Suitable carbonate binders include alkali metal and alkaline earth metal carbonates as described in German Patent Application No. 2,321,001, published November 15, 1973, although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate may also be useful. And other carbonate minerals such as trona or any conventional multiple salt of sodium carbonate and calcium carbonate such as those having the composition 2Na2CO3-CaCC> 3 when in the anhydrous state and even calcium carbonates including calcite, aragonite and vaterite, especially forms having a high surface area as compared to compact calcite, eg as grains for use in synthetic detergent bars .

Suitable organic detergent binders include polycarboxylate compounds, including water-soluble non-surfactant dicarboxylates and tricarboxylates. More typically, polycarboxylates have a plurality of carboxylate groups, preferably at least 3 carboxylates. The carboxylate binder may be formulated in an acidic, partially acidic, neutral or alkaline form. When in the form of salts, alkali metals such as sodium, potassium and lithium or alkanolammonium salts are preferred. Polycarboxylate binders include ether polycarboxylates such as oxydisuccinates; Berg, U. S. 3,128,287, Apr. 7, 1964; and Lamberti et al., U. S. 3,635,830, Jan. 18, 1972; TMS / TDS binders of U. S. 4,663,071, May 5, 1987 (Bush et al.) And other ether carboxylates including cyclic and alicyclic compounds such as those described in U. S. 3,923,679, 3,835,163,4,158,635,4,120,874 and 4,102,903.

Other suitable binders are ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, carboxymethyloxysuccinic acid, various alkali, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid acid, as well as mellitic acid, succinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethylsuccinic acid, and soluble salts thereof.

Citrates such as citric acid and its soluble salts are important carboxylate binders, e.g., for strong liquid detergents, due to their availability from renewable sources and their biodegradability. Citrates can also be used in granular formulations, especially in combination with zeolites and / or layered silicates. Oxydisuccinates are also particularly useful in such compositions and combinations.

Where permitted, and especially in the formulations of solid bars for handwashing, alkali metal phosphates such as sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate may be used. Phosphonate binders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphates, e.g. described in U.S. Patent 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137 can also be used and have suitable properties.

• ·

Some detersive surfactants or their short chain homologues may also have binder properties. For the purpose of unambiguous labeling, where they are due to their surfactant capabilities, these materials are summarized as detersive surfactants. Preferred types for binding properties are illustrated by 3,3-dicarboxy-4-oxa-1,6-hexanedioates and related compounds described in U.S. Patent 4,566,984, Jan. 28, 1986 (Bush). Succinic binders include C5 to C20 alkyl and alkenylsuccinic acids and salts thereof. Succinate binders also include: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate and the like. Lauryl succinates are described in European Patent Application 86200680.5 / 0,200,263, published November 5, 1986. Fatty acids, e.g., C 11 -C 18 monocarboxylic acids, may also be included in the compositions as surfactant / binder alone or in combination with the aforementioned binder, especially citrate and / or a succinate binder, to provide additional binder activity. Other suitable polycarboxylates are described in U. S. 4,144,226, March 13, 1979 (Crutchfield et al.) And in U. S. 3,308,067, 7 March 1967 (Diehl). See also Diehl, U. S. 3,723,322.

Other types of inorganic binder materials that can be used have the formula (M _x ) jCay (CO 3) _z , where x and 1 are integers from 1 to 15, y is an integer from 1 to 10, z is an integer from 2 to 25, Mj are cations, at least one of which is water-soluble and the equation spl is satisfied; = 145 (xj multiplied by the valency Mj) + 2y = 2z, so the formula has an overall neutral charge. These binders are referred to as mineral binders. Hydrating water of anions other than carbonate can be added, provided that the total charge is balanced or neutral. The valency charges of these anions should be added to the right side of the above equation. Preferably, there is a water-soluble cation selected from the group consisting of hydrogen, water-soluble metal, boron, ammonium, silicon and mixtures thereof, more preferably sodium, potassium, hydrogen, lithium, ammonium and mixtures thereof, wherein sodium and potassium are highly preferred. Non-exhaustive examples of non-carbonate anions include those selected from the group consisting of chloride, sulfate, fluoride, oxygen, hydroxide, silicon, dioxide, chromate, nitrate, borate, and mixtures thereof. Preferred binders of this type in their simplest form are selected from the group consisting of Na ₂ Ca (CO ₃ ) ₂ , K ₂ Ca (CO ₃ ) ₂ , Na ₂ Ca ₂ (CO ₃ ) ₃ , NaKCa (CO ₃ ) ₂ , NaKCa ₂ (CO ₃ ) ₃ , K ₂ Ca ₂ (CO ₃ ) ₃ and combinations thereof. A particularly preferred binder material described herein is Na ₂ Ca (CO ₃ ) ₂ in any of its crystal modifications. Suitable binders of the type defined above are further illustrated and include natural or synthetic forms of any combination of the following materials: afghanite, andersonite, ashcroftin, beyerite, burbankite, butschliite, cancrinite, carbocemaite, carletonite, davyn, donnayite Y, fairchildite, ferrisurite, franzinite, gaudefroyite, gaylussit, girvasite, gregoryite, jouravskite, kamphaugite Y, kettnerrit, khanneshite, lepersonnit Gd, liottite, mickelveyite Y, microsommite, mroseite, natrofairchildite, nyerereit, remondite, tec, titanite, sacrofanite, sacrofanite tyrolite, vishnevite and zemkorit. Preferred mineral forms include nyererite, fairchildite and shortite.

Many detergent compositions of the present invention will be buffered, i.e., relatively resistant to pH changes in the presence of acidic dirt. However, other formulations of the invention may have exceptionally low buffering capacity or virtually unbuffered. Techniques for controlling different pHs at recommended user values more generally include the use of not only buffers but also additional alkalis, acids, pH hopping systems, twin containers with separate contents and the like. and are well known to those skilled in the art.

Some preferred formulations of the invention, such as ADD types, include pH adjusting ingredients selected from water-soluble alkaline inorganic salts and water-soluble organic or inorganic binders. The pH adjusting components are selected such that when the ADD dissolves in water at concentrations of from 1,000 to 5,000 ppm, the pH remains in the range of about 8, preferably about 9.5 to about 11. Preferred non-phosphate pH adjusting components may be selected from the group consisting of:

(ii) sodium carbonate or sesquicarbonate, (ii) sodium silicate, preferably hydrated sodium silicate having a ratio between SiO ₂ and Na ₂ O ranging from 1: 1 to about 2: 1 and mixtures thereof with a limited amount of sodium metasilicate, (iii) sodium citrate (iv) citric acid (v) sodium bicarbonate (vi) sodium borate, preferably borax (vii) sodium hydroxide and (viii) mixtures (i) to (vii).

Preferred embodiments of the invention contain low concentrations of silicates (i.e., from 3% to less than 10% SiO ₂ ).

Examples of a highly preferred pH adjusting component system are binary mixtures of granular sodium citrate with anhydrous sodium carbonate and a tri-component granular sodium citrate trihydrate, citric acid and anhydrous sodium carbonate system.

The amount of the pH adjusting component in the compositions used for automatic dishwashing is preferably from 1% to about 50% by weight of the composition. In a preferred embodiment, the component is present in the composition from 5% to about 40%, preferably from 10% to about 30% by weight of the composition.

For compositions of the invention having a pH of between 9.5 and 11 in the original wash solution, particularly preferred ADDs (in weight percent ADD) are from 5% to about 40%, preferably from 10% to about 30%, most preferably from 15% to about 20% sodium citrate with from 5% to about 30%, preferably from 7% to about 25%, most preferably from 8% to about 20% sodium carbonate.

The basic pH adjustment system may be supplemented (i.e., improved in hard water performance) with additional optional detergent binder salts selected from non-phosphate detergent binders known in the art, including various water-soluble alkali metal borates, ammonium or substituted ammonium borate, hydroxysulfonates, polyacetates and polycarboxylates. Also preferred are alkali metal salts of these materials, especially sodium. Alternatively, water-soluble inorganic binders may be used for this purpose. Examples of polyacetates and polycarboxylate binders are the sodium, potassium, lithium, ammonium, and substituted ammonium salts of ethylenediaminetetraacetic acid, nitriloacetic acid, tartrate monosuccinic acid, tartrate disuccinic acid, oxydisuccinic acid, carboxymethoxysuccinic acid, and sodium mellitarboxylic acid, melliticarboxylic acid.

Detergent compositions for automatic dishwashing may further include water-soluble silicates. Water-soluble silicates in the present invention are any silicates that are soluble to the extent that they do not adversely affect the staining or film forming characteristics of the ADD formulations.

Examples of silicates are sodium metasilicate and more generally alkali silicates, especially those having a ratio between SiChiNa10 in the range of 1.6: 1 to 3.2: 1 and layered silicates, such as the layered sodium silicates described in US Patent 4,664,839, issued May 12, 1987 (P. P. Rieck). NaSKS-6® is a crystalline layered silicate sold by Hoechst (usually abbreviated as SKS-6). Unlike zeolite binders, NaSKS-6 and other water-soluble silicates useful in the present invention do not contain aluminum. NaSKS-6 is 6-Na 2 SiO 5 in the form of a layered silicate and can be prepared by methods such as preferred in German DE-A-3,417,649 and DE-A-3,742,043.

• ·

OA ······ u ··· ·· ··· ·· · i

SKS-6 is the preferred silicate for use in the present invention, but other such layered silicates may be used, such as those having the general formula NaMSi _x O 2 _X + ryH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 , preferably 2 and y is a number from 0 to 20, preferably 0. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, such as α-, β- and γforms. Other silicates may also be useful, such as magnesium silicate, which may serve as a brittle agent for granular formulation, as a stabilizer for oxygen bleaches, and as a component of the suds control system.

Silicates particularly useful for use in automatic dishwashing (ADD) include 2 ratio granular hydrated silicates such as BRITESIL® H2O from PQ Corp., and commonly used BRITESIL® H24, although liquid grades of different silicates can be used if ADD preparations have liquid form. Within safe limits, sodium metasilicate or sodium hydroxide alone or in combination with other silicates may be used to raise the wash pH to the desired level.

Polymeric soil release agents

The known polymeric soil release agents, hereinafter referred to as SRAs, may optionally be used in the detergent compositions of the present invention, particularly in detergent compositions. When used, SRAs will generally comprise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight of the composition. Preferred SRAs typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments that deposit on hydrophobic fibers and remain adjacent to them during the wash and rinse cycle thereby serving as an anchor for the hydrophilic segments. This allows stains that occur after SRA to be removed more easily at a later wash.

SRAs can include many charged, e.g., anionic or even cationic (see U.S. 4,956,447) as well as uncharged monomer units, and their structures can be linear, branched, or even star-shaped. They may include bridging units that are particularly effective in controlling molecular weight or changing physical or surface properties. The charge structures and distributions can be tailored to suit different fiber or textile type applications and to different detergents or detergent additive products.

Preferred SRAs include oligomeric terephthalate esters, typically prepared by a process involving at least one transesterification / oligomerization, often with a metal catalyst such as

like titanium alkoxide. Such esters can be made using other monomers capable of incorporation into the ester structure via one, two, three or four positions without producing densely crosslinked resulting structures.

Suitable SRAs include: sulfonated products of substantially linear ester oligomers including the oligomeric ester backbone of terephthaloyl or oxyalkyleneoxy units and allyl-derivatized sulfonated terminal groups that are covalently attached to the backbone, e.g. as described in US 4,968,451, November 6, 1990 (JJ Scheibel and EP Gosselink), these esters can be prepared by (a) ethoxylating allyl alcohol, (b) reacting product (a) with dimethyl terephthalate (DMT) and 1,2-propylene glycol (PG) in a two step transesterification / oligomerization process and (c) reaction of the product ( (b) sodium metabisulphite in water; Non-ionic end-bridged 1,2-propylene / polyoxyethylene terephthalate polyesters US 4,711,730, Dec. 8, 1987 (Gosselink et al.), e.g., those produced by teransesterification / polymerization of poly (ethylene glycol) methyl ether, DMT, PG and poly (ethylene glycol) ( PEG); partially and fully anionic terminal bridged oligomeric esters of U. S. 4,721,580,26. January 1988 (Gosselink) such as oligomers of ethylene glycol (EG), PG, DMT, and Na-3,6-dioxa8-hydroxyoctane sulfonate; nonionic bridged block polyester oligomer compounds of US 4,702,857, Oct. 27, 1987 (Gosselink) produced e.g. from DMT, Me-bridged PEG and EG and / or PG or a combination of DMT, EG and / or PG, Me-bridged PEG and Nadimethyl- 5-sulfoisophthalate and anionic especially sulfoaroyl, end-bridged terephthalate esters according to US 4,877,896, Oct. 31, 1989 (Maldonado, Gosselink et al.), The latter being a typical SRA useful in both laundry and fabric conditioning compositions, an example of which is an ester preparation formed from the monosodium salt of m-sulfobenzoic acid. PG and DMT optionally, however, preferably contain added PEG, eg PEG 3400.

SRAs also include single copolymer polymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate. U, S. 3,959,230, May 25, 1976 (Hays) and U. S. 3,893,929, July 8, 1975 (Basadur); cellulose derivatives such as hydroxyether cellulose polymers available as METHOCEL from Dow and C1 to C4 alkylcelluloses and C4 hydroxyalkylcelluloses; U.S. 4,000,093, Dec. 28, 1976 to Nicol et al. Suitable SRAs characterized by poly (vinyl ester) hydrophobic segments include graft copolymers of poly (vinyl ester), e.g., C 1 -C 6 vinyl esters, preferably poly (vinyl acetate), grafted onto a polyalkylene oxide backbone. See. European Patent Application 0 219 048, published April 22, 1987 (Kud et al.). Commercially available examples include SOKALAN •

SRA such as SOKALAN HP-22, available from BASF, Germany. Other SRAs are repeating unit polyesters containing 10-15% by weight of ethylene terephthalate together with 90-80% by weight of polyethylene terephthalate derived from polyoxyethylene glycol with an average molecular weight of 300 to 5000. Commercial examples include ZELCON 5126 from duPont and MILEASE T from ICT .

Another preferred SRA is an oligomer having the empirical formula (CAP) 2 (EG / PG) with (T) 5 (SIP) i, which includes terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene ( EG / PG) units and which is preferably terminated by terminal groups (CAP), preferably modified with isethionates such as in an oligomer comprising one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethylenoxy and oxy-1,2-propylenoxy units in a defined ratio, preferably 0.5: 1 up to 10: 1, and two end groups derived from sodium 2- (2-hydroxyethoxy) ethanesulfonate. Said SRA preferably further comprises from 0.5% to 20% by weight of an oligomer of a cristalinite-reducing stabilizer, eg an anionic surfactant such as linear dodecylbenzenesulfonate or a member selected from xylene, cumene and toluenesulfonates or mixtures thereof, these stabilizers or modifiers being introduced. to a reaction vessel according to US 5,415,807, issued May 16, 1995 (Gosselink, Pan, Kellett, and Hal). Suitable monomers for the above SRA include Na 2- (2-hydroxyethoxy) ethanesulfonate, DMT, Na-dimethyl 5-sulfoisophthalate, EG and PG.

Another group of preferred SRAs are oligomeric esters comprising: (1) a backbone comprising (a) at least one unit selected from the group consisting of dihydroxysulfonates, polyhydroxysulfonates, a unit that is at least trifunctional, wherein the ester linkages are formed to form a branched oligomer backbone and combination; (b) at least one unit that is a terephthaloyl unit, and (c) at least one non-sulfonated unit that is a 1,2-oxyalkylenoxy unit, and (2) one or more end groups selected from nonionic end groups, anionic end groups such as alkoxylated, preferably ethoxylated, isethionates, alkoxylated propanesulfonates, alkoxylated propane disulfonates, alkoxylated phenolsulfonates, sulfoaroyl derivatives, and mixtures thereof. Such preferred esters are those having the general formula:

{(CAP) _x (EG / PG) / DEG) _y. <PEG), _t <T) _z (SIP) _z <SEG) _q (B) _m} wherein CAP, EG / PG, PEG, T and SIP are as defined above, (DEG) represent di (oxyethylene) oxy units; (SEG) represent units derived from sulfoethyl ether of glycerin and related units, (B) is a branching unit that is at least trifunctionalized, wherein the ester linkages are formed to form a branched oligomer backbone, x being from 1 to about 12, which is from 0.5 to about 25, y is from 0 to about 12, y is from 0 to about 10, y + is from 0.5 to about 25, z is from about 1.5 to about 25, z'is from 0 to about 12, z + z'is from about 1.5 to about 25, q is from 0.5 to about 12, m is from about 0.01 to about 10, and x, y, y, y , z, z ', q and m represent the average number of moles of the corresponding unit per mole of said ester, and said ester has a molecular weight in the range of from 500 to about 5000.

Preferred SEG and CAP monomers for the above ester include Na-2- (2,3-dihydroxypropoxy) ethanesulfonate (SEG), Na-2- {2- (2-hydroxyethoxy) ethoxy} ethanesulfonate (SE3) and homologues thereof, and mixtures and products thereof ethoxylation and sulfonation of allyl alcohol. Preferred SRA esters in this class include the transesterification and oligomerization product of sodium 2- {2- (2-hydroxyethoxy) ethoxy} ethanesulfonate and / or sodium 2- [2- {2- (2-hydroxyethoxy) ethoxy} ethoxy] ethanesulfonate, DMT, sodium 2- (2,3-dihydroxypropoxy) ethanesulfonate, EG and PG using appropriate Ti (IV) catalysts and can be designated as (CAP) 2 (T) ₅ (EG / PG) _i4 (SEG) 2.5 (B 10, where CAP is (Na ⁺ O ₃ S [CH ₂ CH ₂ O] 3, ₅ ) - and B is a unit of glycerin and the EG / PG molar ratio is about 1.7: 1 as measured by conventional gas chromatography after complete hydrolysis.

Another class of SRA includes (I) nonionic terephthalates using diisocyanate coupling agents to form a polymeric ester structure; US 4,201,824 (Violland et al.) And US 4,240,918 (Lagasse et al.); (Π) SRAs with carboxylate terminal groups prepared by adding trimellitic anhydride to the known SRA, wherein the terminal hydroxyl groups are converted to trimellitic acid esters. Appropriate selection of the catalyst forms trimellitic anhydride by coupling to the ends of the polymer via the isolated carboxylic acid esters of trimellitic anhydride rather than by opening the anhydride coupling. Both nonionic and anionic SRAs can be used as starting materials if they have terminal hydroxyl groups that can be esterified. See. US 4,525,524 to Tung et al. (ΙΠ) anionic terephthalate-based SRAs with urethane couplings; US 4,201,824 (Violland et al.); (IV) poly (vinylcaprolactam) and related copolymers with monomers such as vinylpyrrolidone and / or dimethylaminoethyl methacrylate, including both non-ionic and cationic polymers; US 4,579,681 (Rupert et al.); (V) graft copolymers, other than SOKALAN types from BASF, made by grafting acrylic monomers to sulfonated polyester; these SRAs are said to have the effectiveness of removing dirt and preventing it from settling, similar to known cellulose ethers: cf. EP 279,134 A, 1988 ¹⁰⁰ (Rhone-Poulenc Chemie); (VI) grafts of vinyl monomers such as acrylic acid and vinyl acetate to proteins such as casein; EP 457,205 A, 1991 (BASF); (VII) polyester polyamide SRAs prepared by condensation of adipic acid, caprolactam and polyethylene glycol, in particular for the treatment of polyamide fibers, cf. Bevan et al., DE 2,335,044, 1974 (Unilever NV). Other suitable SRAs are described in US Patent 4,240,918, 4,787,989 and 4,877,896.

Agents to remove soil stains and prevent them from settling

The compositions of the present invention may optionally contain water-soluble ethoxylated amines which act to remove clay stains and prevent their re-settling. Granular detergent compositions containing these compounds typically contain from about 0.01% to about 10.0% by weight of water-soluble ethoxylated amines; liquid detergent compositions typically comprise from 0.01% to about 5%.

The preferred clay stain removal and antifouling agent is ethoxylated tetraethylenepentamine. Examples of ethoxylated amines are further described in U.S. Patent 4,597,898, issued July 1, 1986 (VanderMeer). Another group of preferred clay stain removal and anti-redeposition agents are the cationic compounds disclosed in European Patent Application 111,965, published June 27, 1984 (Oh and Gosselink). Other clay stain removal and re-settling agents that can be used in the present invention include the ethoxylated amine polymers described in European Patent Application 111,984, published June 27, 1984 (Oh and Gosselink); zwitterionic polymers disclosed in European Patent Application 112,592, published July 4, 1984 (Gosselink), and amine oxides described in U.S. Patent 4,548,744, issued October 22, 1985 (Connor). Other clay stain removing and antifouling agents known in the art may also be used in the compositions of the present invention. See. U.S. Patent 4,891,160, issued Jan. 2, 1990 (VanderMeer) and WO 95/32272, published Jan. 30, 1995. Another type of preferred re-settling agents include carboxymethylcellulose (CMC) materials. These materials are well known in the art.

Polymeric dispersing agents

Polymeric dispersing agents may advantageously be used at concentrations of from about 0.1% to about 7% by weight of the composition of the invention, especially in the presence of zeolite.

101 and / or layered silicate binders. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although other agents known in the art may be used. Although not believed to be bound by the theory, polymer dispersants enhance the overall binder action when used in conjunction with other binders (including low molecular weight polycarboxylates) by preventing crystal growth, promoting the release of dirt particles, and preventing their resettling.

Polymeric carboxylate 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), filmic acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, and methylenemalonic acid. The presence of the polymeric polycarboxylates of the present invention or monomeric segments containing no carboxylate radicals such as vinyl methyl ether, styrene, ethylene and the like is suitably ensured such that the segments do not constitute more than 40% by weight.

Particularly suitable polymeric polycarboxylates may be derived from acrylic acid. The acrylic acid-based polymers useful herein are water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers preferably ranges from about 2000 to 10000, more preferably from about 4000 to 7000, and most preferably from 4000 to about 5000. Water-soluble salts of these acrylic acid-based polymers may include, for example, alkali, ammonium, and substituted ammonium, λ / worthy polymers of this type are known materials. The use of polyacrylates of this type in detergent compositions has been described, for example, in Diehl, U.S. Patent 3,308,067, issued March 7, 1967.

Acrylic / maleic acid copolymers can also be used as the preferred components of dispersants and anti-settling agents. The average molecular weight of these copolymers in acid form is preferably from 2000 to about 100000, more preferably from 5000 to 75000, most preferably from about 7000 to 65000. The ratio of acrylate and maleic segments in these copolymers will generally be in the range of 30: 1 to about 1: 1, more preferably from about 10: 1 to 2: 1. Odo-soluble salts of these acrylate and maleic copolymers may include, for example, alkali metals, ammonium, and substituted ammonium salts. Soluble acrylate and maleic copolymers of this type are known materials and are described in European Patent Application 66915, published December 15, 1982, as well as in the EP.

In Ar ··· ·· ··· · · · ·

193,360, published Sep. 3, 1986, which also discloses such polymers including hydroxypropyl acrylates. Other useful dispersing agents include maleic terpolymers

/ acrylic acid / vinyl alcohol. These materials are also described in EP 193,360, including, for example, a 45/45/10 acrylic / maleic / vinyl alcohol terpolymer.

Another polymeric material that can be utilized is polyethylene glycol (PEG). PEG can act as a dispersant as well as play a role of soil release agent and prevent re-settling. Typical molecular weight ranges for these purposes are from about 500 to about 100,000, preferably from about 1000 to about 50,000, more preferably from about 1500 to about 10,000.

Polyaspartate and polyglutamic dispersing agents can also be used, especially in conjunction with zeolite binders. Dispersing agents such as polyaspartates preferably have an average molecular weight of about 10,000.

Other types of polymers that may be suitable for their biodegradability, increased bleach stability or cleansing performance include various terpolymers and hydrophobically modified copolymers, including those sold by Rohm & Haas, BASF Corp., Nippon Shokubai and others for all kinds of textile processing. or detergent applications.

Brighteners

Any optical brightener or other brightening or bleaching agent known in the art may be included in the compositions of the present invention at concentrations typically from about 0.01% to about 1.2% by weight of the composition when designed to wash fabrics. Commercial optical brighteners that may be useful in the present invention may be classified into subgroups including, but not limited to, derivatives of stilbene, pyrozoline, coumarin, carboxylic acids, methinkyanines, dibenzothiophene-5,5-dioxide, azoles, and 6-membered heterocyclic rings and other miscellaneous reagents. Examples of these brighteners are described in "The Production and Application of Fluorescent Brightening Agents," by M. Zahradnik, published in John Wiley & Sons, New York (1982). ·

Specific examples of optical brighteners useful in the compositions of the invention are those described in U.S. Patent 4,790,856, issued December 13, 1988 (Wixon). These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners described in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5MB, available from Ciba-Geigy; Arctic White CC and Arctic White CWD, 2- (4-styrylphenyl) -2H-naphtho [1,2] ·

103

di-triazoles, 4,4´-bis (1,2,3-triazol-2-yl) stilbenes; 4,4´-bis (styiyl) bisphenyls and aminocoumarins. Particular examples of these brighteners include 4-methyl-7-diethylamino-knuarin, 1,2bis (benzimidazol-2-yl) ethylene, 1,3-diphenylpyrazolines, 2,5-bis (benzoxazol-2-yl) thiophene, 2-styryl naphtho [1,2] -d] oxazole and 2- (stilben-4-yl) -2H-naphtho [1,2-d] triazole. See. also U.S. Patent 3,646,015, issued February 29, 1972 (Hamilton).

Color transfer agents

The compositions of the invention may also include one or more materials effective to inhibit the transfer of dyes from one fabric to another during the cleaning process. Generally, these dye transfer agents from one fabric to another include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, magnesium phthalocyanine, peroxidases, and mixtures thereof. When used, these agents typically comprise from 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%, and most preferably from 0.05% to about 2%.

More specifically, the polyamine N-oxide polymers preferred for use in the present invention comprise units having the following structural formula: RA _x -P, where P is a polymerizable unit to which an N-O group may be attached or the N-O group may be part of a polymerizable unit or an N-O group may be attached to both units, A is one of aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof to which an N-O group may be attached or the N-O group may be part of of these groups. Preferred polyamine oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.

The N-O group may be represented by the following general formulas:

OO ( ^{R 1} ) _x -N- (RA; = N- (R 1) _x (R ₃ ) z wherein R 1, R ₂ and R ₃ are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z they are 0 or 1 and the nitrogen in the N-O group may be attached or may be part of the above groups The amine oxide unit of the polyamine N-oxides has a pKa <10, preferably pKa <7, most preferably pKa <6.

104 • · · ·

Any polymer backbone can be used as long as the amine oxide polymer is water-soluble and has an effect in preventing color transfer. Examples of suitable polymer backbones are polyvinyl, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers wherein one monomer unit is an amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide polymers typically have a ratio between amine and amine N-oxide of 10: 1 to 1: 100000. However, the number of amine oxide groups present in the polyamine oxide polymer can vary by appropriate copolymerization or varying degrees of N-oxidation. Polyamine oxides can be obtained at virtually any degree of polymerization. Typically, the average molecular weight is in the range of 5,000 to about 100,000. This preferred class of materials may be referred to as "PVNO".

The most preferred polyamine N-oxide useful in the detergent compositions of the invention is poly (4-vinylpyridine-N-oxide) having an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1: 4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole (referred to as the class "PVPVI") are also preferred for use in the present invention. Preferably, the PVPVI has an average molecular weight ranging from 5,000 to 10,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range was determined by light scattering as described by Bart et al., Chemical Analysis, vol. 113). Modem Methods of Polymer Characterization ”, which is incorporated herein by reference). PVPVI copolymers typically have a molar ratio of N-vinylpyrrolidone to N-vinylimidazole of from 1: 1 to 0.2: 1, more preferably from 0.8: 1 to 0.3: 1, and most preferably from 0.6: 1 to 0.4: 1. These copolymers may be either linear or branched.

The compositions of the invention may also use polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5000 to about 400000, preferably from 5000 to about 200000, and most preferably from 5000 to about 50,000. PVPs are known to those skilled in the detergent art. eg EP-A-262897 and EP-A-256696, incorporated herein by reference. Formulations containing PVP may also contain polyethylene glycol ("PEG") having an average molecular weight of from 500 to about 100,000, preferably from 1000 to about 10,000. Preferably, the ratio between PEG and PVP based on ppm in the wash solution is from 2: 1. to about 50: 1, and more preferably from about 3: 1 to about 10: 1.

The detergent compositions of the invention may also optionally comprise from 0.005% to 5% by weight of some types of hydrophilic optical brighteners that also provide inhibition

105 v v ♦ · · · v v v v v v v v v v v v v v v v v v • v v • Color Transmission. If used, they will preferably contain from 0.01% to 1% by weight of such an optical brightener.

Hydrophilic optical brighteners useful in the present invention include those having the general formula:

wherein R 1 is selected from anilino, N-2-bishydroxyethyl and NH-2-hydroxyethyl, R ₂ is selected from N-2-bishydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino and M is a salt-forming cation such as like sodium or potassium.

When in the above formula, Rl is anilino, _R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4'-bis [4-anilino-6- (N-2-bis-hydroxyethyl) -s- triazin-2-yl) amino] 2,2'-stilbenedisulfonic acid and its sodium salt. This particular brightener is commercially marketed under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPAGX is a preferred hydrophilic optical brightener useful in the compositions of the present invention.

When in the above formula, Rl is anilino, _R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4,4'-bis [4-anilino-6- (N-2 (hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid and its sodium salt. This particular brightener is commercially marketed under the trade name Tinopal-5BM-GX by Ciba-Geigy Corporation.

When R ₁ is anilino, R ₂ is morpholino and M is a cation such as sodium in the above formula, the brightener is 4,4'-bis [(4-anilino-6-morpholino-s-triazin-2-yl) amino] - 2,2'-stilbenedisulfonic acid and its sodium salt. This particular brightener is commercially marketed under the trade name Tinopal-AMS-GX by Ciba-Geigy Corporation.

Certain optical brighteners selected for use in the present invention provide particularly effective color transfer inhibition when combined with the selected color transfer inhibiting agents described above. The combination of these selected polymeric materials (eg, PVNO and / or PVPVI) with these selected optical brighteners (eg, Tinopal UNPA-GX, Tinopal 5BM-GX and / or Tinopal AMS-GX) provides significantly better inhibition of color transfer in aqueous wash solutions than this is the case with individual components when used separately. Without us

106

felt to be bound by theory, the degree of clarifier settling on the fabric in the wash solution can be defined by a parameter called the "exhaust coefficient". The exhaust coefficient is generally defined as the ratio of a) the brightener material deposited on the fabric to b) the original brightener concentration in the wash solution. Brighteners with a relatively high exhaust coefficient are most suitable for inhibiting the color transfer of the present invention.

Other conventional optical brighteners may optionally be used in the compositions of the present invention to provide conventional "brightener" effects, rather than for their color transfer inhibition effect. This use is conventional and well known in the detergent art.

Chelating agents

The detergent compositions of the present invention may also optionally contain one or more chelating agents, especially chelating agents for randomly occurring transition metals. Metals commonly found in wash water include iron and / or manganese in a water-soluble, colloidal or particulate form, and may be in the form of oxides or hydroxides or may be found in conjunction with shumines. Preferred chelants are those which effectively control such transition metals, especially when they also control the deposition of these transition metals or their compounds on fabrics and / or control unwanted redox reactions in laundry solutions and / or on fabrics or solid surfaces. These chelating agents include substances having low molecular weight as well as polymer types, typically having at least one, preferably two or more heteroatoms such as O or N, capable of coordinating to a transition metal. Conventional chelating agents may be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionalized substituted aromatic chelating agents, and mixtures thereof, all of which are defined below.

Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethylethylenediaminetetraacetates, nitrilotriacetates, ethylenediaminetrapropionates, triethylenetetraamine hexaacetates, diethylenetriaminepentaacetates and ethanediglycones, their alkali metal salts and their ammonium salts, and their alkali metal salts.

Aminophosphonates are also suitable for use as chelating agents in the compositions of the present invention when at least a low degree of phosphorus is permitted in detergent compositions and include ethylenediaminetetrakis (methylene phosphonates) such as DEQUEST. Preferably, these

107 »Aminophosphonates do not contain alkyl groups or alkenyl groups having more than about 6 carbon atoms.

Polyfunctionally substituted aromatic chelating agents are also useful in the compositions of the invention. See. U.S. Patent 3,812,044, issued May 21, 1974 to Connor et al. Preferred compounds of this type in acid form are dihydroxysulfobenzenes such as 1,2dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelator for use in the present invention is ethylenediamine disuccinate ("EDDS"), especially the [S, S] isomer as described in U. S. Patent 4,704,233 of November 3, 1987 to Hartman and Parkins.

The compositions of the present invention may also contain water-soluble salts of methyl glycine diacetic acid (MGDA) (or its acid form) as a chelating agent or as a binder useful with, e.g., insoluble binders such as zeolites, layered silicates, and the like.

When used, chelating agents will generally comprise from about 0.001% to about 15% by weight of the detergent composition of the invention. More preferably, the chelating agents will comprise from about 0.01% to about 3.0% by weight of such compositions.

Soap suppressants

Soap-reducing or anti-suds suppressors can be included in the compositions of the present invention if desired, particularly in laundry washing. Other formulations, such as those intended for handwashing, may be intentionally high soap suds, and these ingredients may be completely disregarded. Soap suppressants can be of particular importance in so-called "highly concentrated cleaning processes" as described in U.S. Pat. Nos. 4,489,455 and 4,489,574 and in European pre-load automatic washing machines.

Many materials known in the art can be used as suds suppressors. See. eg, Kirk Othmer Encyclopedia of Chemical Technology, third edition, vol. 7, pp. 430-447 (Wiley, 1979). Monocarboxylic fatty acids and their salts are commonly used. See. U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John. These are typically hydrocarbon chains of 10 to 24, preferably 12 to 18, carbon atoms. Suitable salts include alkali metal salts such as potassium and lithium, ammonium and alkanolammonium salts.

Other suitable suds suppressors include high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., triglycerides of fatty acids), esters of monovalent fatty acid alcohols, aliphatic C 18 to C 40 ketones (e.g., stearone), and

108 · ti ti ti ti ti ti ti tr tr tr tr tr tr tr tr tr tr tr tr 9 tr tr tr tr tr · II pod. Other suds suppressors include N-alkylated aminotriazoles and monostearyl phosphates such as monostearyl alcohol phosphate ester, di-alkali monostearyl phosphates (e.g., K, Na and Li) and other phosphate esters. The hydrocarbons, such as paraffin and haloparaffin, may be in liquid form, eg, liquid at room temperature and atmospheric pressure with a freezing point in the range of -40 ° C to about 50 ° C and a minimum boiling point of not less than about 110 ° C. . It is also known to use wax hydrocarbons, preferably having a melting point below about 100 ° C. Hydrocarbon suds suppressors are described, for example, in U. S. 4,265,779. Suitable hydrocarbons include aliphatic, alicyclic, aromatic and heteroaromatic saturated or unsaturated O 2 to C 70 hydrocarbons. Paraffins including mixtures of true paraffins and cyclic hydrocarbons may be used.

Silicone suds suppressors may be useful, including polyorganosiloxane oils such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles, wherein the polyorganosiloxane is chemisorbed on the silica gel surface. See U.S. Patent 4,265,779, European Patent Application No. 89307851.9, published February 7, 1990 (Starch M. S.) and U.S. Patent 3,455,839. Mixtures of silicone and silanated silica gel are also described, for example, in German patent application DOS 2,124,526. Silicone antifoams and suds suppressants in granular detergent compositions are disclosed in U.S. Patent 3,933,672 and U.S. Patent 4,652,392.

Examples of silicone suds suppressors for use in the present invention are used in soap suds suppressing amounts and include:

(i) a polydimethylsiloxane liquid having a viscosity of from about 20 cs to about 1500 cs at 25 ° C; (ii) from 5 to about 50 parts per 100 parts by weight of (i) a siloxane resin composed of (CH ₃ ) ₃ SiO _1/2 units and SiO 2 units in a ratio of from about 0.6: 1 to about 2: 1 (iii) from 1 to about 20 parts per 100 parts by weight (i) of solid silica gel.

In preferred silicone suds suppressors, the continuous phase solvent is made from certain polyethylene glycols or polyethylene polypropylene glycol copolymers or mixtures thereof (preferred) or polypropylene glycol. Primary suds suppressors are branched / crosslinked. Typical liquid laundry detergent compositions with suds suppressors include from about 0.001 to about 1, preferably from about 0.01 to about 0.7, and most preferably from about 0.05 to about 0.5.

109% by weight of said suds suppressor silicone agent, comprising (1) non-aqueous emulsions of primary antifoam agents, which is a blend (a) a polyorganosiloxane, (b) a silicone resin-producing silicone resin or silicone resin-producing compound, (c) a finely divided filler material, and (d) a catalyst to react the mixture of (a), (b) and (c) to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a polyethylene-polypropylene glycol copolymer having a water solubility at room temperature greater than about 2% by weight and free of polypropylene glycol. Similar amounts may be used in granular preparations, gels and the like. See also US Patent 4,978,471, issued December 18, 1990 (Starch) and 4,983,316, issued January 8, 1991 (Starch), 5,288,431 issued February 22, 1994 (Huber et al.), And US Patent 4,639,489 and 4,749,740 (Aizawa et al.) in column 1, line 46 through column 4, line 35.

The silicone suds suppressors preferably include polyethylene glycol and a polyethylene glycol / polypropylene glycol copolymer, all having an average molecular weight of less than about 1000, preferably between 100 and 800. The polyethylene glycol and polyethylene / polypropylene copolymers of the present invention have a water solubility at room temperature above about 2% by weight, preferably greater than about 5% by weight.

A preferred solvent of the invention is polyethylene glycol having an average molecular weight of less than 1000, more preferably in the range of about 100 to 800, most preferably 200 to 400, and a polyethylene glycol / polypropylene glycol copolymer, preferably PPG 200 / PPG300. Preferred is a weight ratio between 1: 1 and 1:10, most preferably between 1: 3 and 1: 6 polyethylene glycol: polyethylene glycol-polypropylene glycol copolymer.

The preferred suds suppressor silicone agents used in the present invention do not contain polypropylene glycol, especially having a molecular weight of 4000. They also preferably do not contain block copolymers of ethylene glycol and propylene glycol such as PLURONIC L101.

Other suds suppressors of the present invention include secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of these alcohols with silicone oils such as those described in U.S. Pat. S. 4,798,679, 4,075,118 and EP 150,872. Secondary alcohols include C 6 -C 16 alcohols having a C 1 -C 16 chain. A preferred alcohol is 2-butyloctanol, which is available from Condea under the trade name ISOFOL 12. Mixtures of secondary alcohols are available under the trade name ISALCHEM 123 from Enichem. Mixing suds suppressors include alcohol + silicone mixtures in a weight ratio of 1: 5 to 5: 1.

• 9 • ·

110 »· · (» · «<

• 1 · 1

• · · ·

Any detergent intended for automatic laundry washing should not form soaps to overfill the washing machine. Soap suppressing agents, when used, are preferably in a "soap suppressing amount". By this term it is meant that when formulating the composition, an amount of suds suppressant can be selected which will sufficiently control the suds formation so that the automatic laundry laundry detergent composition will form few suds.

The compositions of this invention will generally contain from 0% to about 10% of suds suppressors. When such agents are used, the monocarboxylic fatty acids and their salts will typically be used in concentrations up to 5%, preferably from 0.5% to 3% by weight of the detergent composition, although other agents may be used. Preferably, from 0.01% to about 1% of a silicone suds suppressor is used, more preferably from 0.25% to about 0.5%. These weight percentages include any silicate that can be used in combination with a polyorganosiloxane, as well as any suds suppressant that can be used as a filler material. Monostearyl phosphate suds suppressors are generally used in amounts ranging from 0.1% to about 2% by weight of the composition. Hydrocarbon suds suppressors are typically used in amounts ranging from about 0.01% to about 5.0%, although higher concentrations may be used. Alcoholic suds suppressors are typically used in concentrations of from 0.2% to 3% by weight of the finished composition.

Soap suppression systems are also useful in the automatic dishwashing (ADD) of the present invention. Silicone suds suppressors and other antifoam agents for all purposes of the present invention are widely documented in "Defoaming, Theory and Industrial Applications", Ed. Garrett, P.R., Marcel Dekker, New York, 1973, ISBN 0-8247-87706, incorporated herein by reference. See, in particular, the chapters entitled "Control of foaming in detergent products" (Ferch et al.) And "Surfactant antifoams" (Blease et al.). See also U.S. Patent 3,933,672 and 4,136,045. Highly preferred suds suppressors for ADD applications include composite types known from use in laundry detergents such as high performance granules, although the hitherto used types in high performance liquid detergents can also be used in the compositions of the invention. For example, polydimethylsiloxanes having a trimethylsilyl or alternating terminal blocking group may be used as silicone. These may be comprised of silica gel and / or a non-silicone surfactant component, as illustrated by suds suppressors, including 12% silicone / silica gel, 18%.

111% stearyl alcohol and 70% starch in granular form. A suitable commercial source of silicone active compounds is Dow Corning Corp.. When the use of phosphate esters is permitted, suitable compounds are described in U.S. Pat. S. Patent 3,314,891, issued April 18, 1967 to Schmolka et al., Incorporated herein by reference. Preferred alkyl phosphate esters contain from 16 to 20 carbon atoms. Highly preferred alkyl phosphate esters are acid monostearyl phosphate or acid monooleyl phosphate or salts thereof, especially alkali metal salts or mixtures thereof. It has been found better to avoid the use of simple calcium precipitating soaps as anti-foaming agents in ADD formulations as they tend to deposit on the surface of the dishes. Indeed, the phosphate esters are not completely free from these problems, and in the formulation of formulations, a minimum content of these substances potentially settling in ADD uses is usually preferred.

Alkoxylated polycarboxylates

Alkoxylated polycarboxylates, such as those prepared from polyacrylates, are useful in the present invention as they provide an additional fat removal effect. These materials are described in WO 91/08281 and PCT 90/01815, which are incorporated herein by reference. Chemically, these materials include polyacrylates having one side ethoxy chain per 7-8 acrylate units. The side chains have the formula - (CH 2 CH 2 O) _m (CH 2) _n CH 3 where m is 2 to 3 and _n is 6 to 12. The side chains are ester-linked to the polyacrylate "backbone" to provide a "comb" structure of the polymer. The molecular weight may vary, but typically ranges from about 2000 to about 50,000. Such alkoxylated polycarboxylates may comprise from about 0.05% to about 10% by weight of the composition of the invention.

Fabric softeners

Optionally, various fabric softeners, especially very fine smectic clays according to US Patent 4,062,647, issued December 13, 1977 (Storm and Nirschl), as well as other fabric softeners known in the art, typically at levels from about 0.5% to about 10% by weight of the composition of the present invention to provide fabric softening effects together with fabric cleaning. Clay softeners can be used in combination with amine or cationic softeners as described in U.S. Patent 4,375,416, issued March 1, 1983 (Crisp et al.) And U.S. Patent 4,291,071, issued September 22, 1981 (Harris et al.). In addition, in the laundry methods of the present invention, fabric softeners, including biodegradable types, may be used in the pre-wash, main wash, post-wash or drying mode.

Perfumes

Perfumes and perfume ingredients useful in the compositions of the present invention and processes include a wide variety of natural or synthetic chemical ingredients including, but not limited to, aldehydes, ketones, esters, and the like. Also included are various natural extracts and essences that may contain complex mixtures of ingredients such as orange oil, lemon oil, rose extract, lavender, musk, patchouli essential oil, balsam essence, sandalwood oil, pine oil, cedar and the like. Final perfumes typically comprise from about 0.01% to about 2% by weight of the composition of the present invention, and the individual perfume ingredients may comprise from 0.0001% to about 90% of the finished perfume composition.

Non-limiting examples of perfume ingredients useful in the compositions of the present invention include: 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene, ionone methyl, ionone gamamethyl, methylcedrylon, methyl dihydrojasmonate, methyl 1,6,10-trimethyl-2,5,9-cyclododecatrien-1-yl ketone, 7-acetyl-1,1,3,4,4,6-hexamethyltetralin, 4-acetyl-6-tert-butyl- 1,1-dimethylindane, p-hydroxyphenylbutanone, benzophenone, methyl beta-naphthylketone, 6-acetyl-1,1,2,3,3,5-hexamethylindane, 5-acetyl-3-isopropyl-1,1,2,6-tetramethylindane , 1-dodecanal, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde, 7-hydroxy-3,7-dimethyloctanal, 10-undecen-1-al, isohexenylcyclohexenylcarboxaldehyde, formyltricyclodecane, hydroxycitroneol condensation products and methylanthranilate, condensation products of hydroxycitronellel and indole, condensation products of phenylacetaldehyde and indole, 2-methyl-3- (tert-butylphenyl) propionaldehyde, ethylvanillin, heliotropin, hexylcinnamic aldehyde, amylcinnamov Aldehyde, 2-methyl-2- (p-isopropylphenyl) propionaldehyde, coumarin, decalactone gamma, cyclopentadecanolide, 16-hydroxy-9-hexadecenoic acid lactone, 1,3,4,6,7,8hexahydro-4,6,6 , 7,8,8-hexamethylcyclopenta-gamma-2-benzopyran, beta-naphtholmethylether, ambroxan, dodecahydro-3a, 6,6,9a-tetramethylnaphtho [2,1b] furan, cedrole, 5- (2,2,3-trimethylcyclopent- 3-enyl) -3-methylpentan-2-ol, 2-ethyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) 2-buten-1-ol, caryophyllene alcohol, tricyclodecenyl propionate, tricyclodecenyl acetate, benzyl salicylate, cedryl acetate and p- (tert-butyl) cyclohexyl acetate.

Particularly preferred materials are those which provide the greatest odor enhancement in the cellulase-containing end products. These perfumes include, but are not limited to:

113 • · hexylcinnamic aldehyde, 2-methyl-3- (p-tert-butylphenyl) propionaldehyde, 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7- tetramethylnaphthalene, benzylsalicylate, 7-acetyl-1,1,3,4,4,6-hexamethyltetralin, p-tert-butylcyclohexyl acetate, methyldihydrojasmonate, beta-naphtholmethyl ether, methyl beta-naphthyl ketone, 2-methyl-2- (p-isopropylphenyl) propionaldehyde, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyran, dodecahydro-3a, 6,6,9a-tetramethylnaphtho [2,1b] furan, anisaldehyde, coumarin, cedrole, vanillin, cyclopentadecanolide, tricyclodecenylacetate and tricyclodecenyl propionate.

Other perfume materials include base oils, resinoids and resins from a variety of sources including (but not limited to) Peruvian balsam, Olibanum resin, styrax, labdan resin, nutmeg, cinnamon oil, benzoin resin, coriander, and lavender. Other perfume chemicals include phenylethyl alcohol, terpineol, linalool, linalylacetate, geraniol, nerol, 2- (1,1-dimethylethyl) cyclohexanol acetate, benzyl acetate and eugenol. Carriers such as diethyl phthalates may be used in the final perfume products.

Care agents

Formulations of the present invention designed for automatic dishwashing may contain one or more treatment agents that are effective as corrosion inhibitors and / or protease agents. These materials are the preferred ingredients of automatic dishwashing compositions, especially in some European countries where the use of electrically silvered nickel and sterling silver plates or the protection of aluminum with low silicon content is still relatively common. Generally, these treating agents include metasilicates, silicates, bismuth salts, manganese salts, paraffin, triazoles, pyrazoles, thiols, mercaptans, aluminum fatty acid salts, and mixtures thereof.

If present, these protective materials are preferably included at low concentrations, eg, from 0.01% to about 5% of the ADD formulations. Suitable corrosion inhibitors include paraffin oil, typically most branched aliphatic hydrocarbons having carbon numbers ranging from about 20 to 50, preferred paraffins are selected from mostly branched C25 to C45 particles having a cyclic to non-cyclic hydrocarbon ratio of about 32:68. Paraffin oil meeting these characteristics is sold by Wintershall, Salzbergen, Germany, under the trade name WINOG 70. In addition, the addition of low concentrations of bismuth nitrate (B1 1) 3 is also preferred.

• ·

Other corrosion inhibitors include benzotriazole and the like, mercaptans or thiols including thionaphthol and thioantranol and finely divided fatty acid aluminum salts such as aluminum tristearate. When formulating the composition, one of ordinary skill in the art will recognize that these materials need to be used wisely and in limited amounts to avoid the tendency to stain or film on the surface of the glassware or to counteract the bleaching effect of the composition. For these reasons, conventional calcium-precipitating fatty carboxylic acids should preferably be avoided and mercaptin protimatic agents that are highly reactive are preferred.

Other ingredients

A wide variety of other ingredients may be included in the compositions of the present invention, including other active ingredients, carriers, hydrotropes, excipients, dyes or pigments, solvents for liquid formulations, solid fillers for solid formulations and the like. If strong foaming is desired, suds activators such as C 10 to C 16 alkanolamides may be included in the compositions of the invention, typically at concentrations of from 1% to 10%. C10 to C14 monoethanol and diethanolamides illustrate a typical class of these suds activators. The use of these suds activators with the high sudsing additional surfactants such as the amine oxides, betaines and sultaines mentioned above is also preferred. If desired, water-soluble magnesium and / or calcium salts such as MgCl ₂ , MgSO 4, CaCl ₂ , CaSO ₄ and the like can be added. at levels of 0.1% to 2% to provide additional soaps and to increase the fat removal effect, especially of liquid dishwashing compositions.

The various detersive ingredients used in the compositions of the present invention may optionally be further stabilized by absorbing said ingredients into the porous hydrophobic substrates, then coating said substrate with a hydrophobic coating, preferably the detersive ingredients are mixed with the surfactant prior to absorption into the porous material. In use, the detersive ingredient is released from the substrate into an aqueous wash solution where it performs its intended detersive function.

To illustrate this technique in more detail, the porous hydrophilic silica (trade mark SIPERNAT D10, Degussa) is mixed with a proteolytic enzyme solution containing 3% to 5% C13 to C15 ethoxylated alcoholic (EO 7) nonionic surfactant. Typically, the enzyme / surfactant solution is 2.5 x the weight of silica gel. The resulting powder is dispersed by stirring in silicone oil (various silicone oils with viscosities in the range of 500 to 12500 may be used). The resulting dispersion in silicone oil is emulsified or otherwise added to the final dispersion.

11C &quot; detergent matrices &quot;, &quot; detergent matrices &quot;. In this way, ingredients such as the aforementioned enzymes, bleaches, bleach activators, transition metal bleach catalysts, organic bleach catalysts, photoactivators, dyes, fluorescent agents, fabric conditioners, hydrolysable surfactants and mixtures thereof for use in detergents, including liquid detergents, may be protected. laundry detergent preparations.

Liquid detergent compositions may contain water and other solvents as carriers. Examples are low molecular weight primary or secondary alcohols such as methanol, ethanol, propanol and isopropanol. Monohydric alcohols are preferred as solubilizing surfactants, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxyl groups (e.g., 1,3-propanediol, ethylene glycol, glycerin and 1,2-propanediol) can also be used. The compositions may contain from 5% to 90%, typically from 10% to 50%, of such carriers.

The detergent compositions of the present invention will preferably be formulated such that, during use in aqueous cleaning operations, the water has a pH in the range of about 6.5 to about 11, preferably from 7 to 10.5, more preferably from 7 to about 9.5. Liquid dishwashing formulations will preferably have a pH between about 6.8 and 9.0. Detergent compositions are typically at pH 9-11. Techniques for controlling pH at recommended levels of use include the use of buffers, alkalis, acids, and the like. and are well known to those skilled in the art.

Form of preparations

The compositions of the present invention may take many physical forms including granular, tablet, bar and liquid forms. The compositions include so-called concentrated granular detergent compositions adapted to be added to the washing machine by dispersing devices disposed in the drum of a washing machine filled with dirty laundry.

The mean particle size of the components of the granular composition according to the invention should be such that no more than 5% of the particles are larger than 1.7 mm in diameter and no more than 5% of the particles are smaller than 0.15 mm in diameter.

The term mean particle size as defined herein is calculated by sieving a sample of the formulation through a number of fractions (typically 5 fractions) per series of Tyler sieves. The weight of the fractions thus obtained is plotted against the size of the screen openings. The mean particle size is taken as the size of the holes through which 50% of the sample weight would pass.

• ·

116

Some preferred granular detergent compositions in accordance with the present invention are high density types now commercially available, these typically having a high density of at least 600 g / l, more preferably from 650 g / l to 1200 g / l.

Agglomeration of surfactants into particles

One preferred method of delivering surfactants in consumer products is to produce agglomerated surfactant particles which may be in the form of flakes, noodles, tapes but preferably in the form of granules. A preferred method of making the particles is by means of agglomerating powders (eg aluminosilicate, carbonate) with a highly active surfactant paste and particle size control of the resulting agglomerate according to specified limits. The process involves mixing an effective amount of a powder with a highly active surfactant paste in one or more agglomerator such as a bowl agglomerator, a mixer with a Z-shaped or more preferably a line mixer such as one manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad , Netherlands and Gebruder Lódige Maschinenbau GmbH, D-4790 Paderbom 1, Elsenerstrasse 7-9, Postfach 2050, Germany. Most preferred is the use of a high shear mixer such as Lodige CB (trade name).

Typically, a highly active surfactant paste comprising from 50% to 90% by weight, preferably 70% to 85% by weight of surfactants is used. The paste may be pumped into the agglomerator at a temperature high enough to maintain a viscosity sufficient to pump, but low enough to avoid degradation of the anionic surfactant used. The operating temperature of the paste is typically 50 ° C to 80 ° C.

Washing methods

The laundry laundry methods of the present invention typically include treating the soiled laundry with an aqueous laundry solution in a laundry machine in which an effective amount of the laundry detergent composition of the present invention is dissolved or dispersed. By an effective amount of a detergent composition is meant from 40 g to 300 g of product dissolved or dispersed in a wash solution in a volume of 5 to 65 liters, which are typical doses of the product and wash solution commonly used in conventional washing methods.

As already mentioned, surfactants are used herein in detergent compositions preferably in combination with other detersive surfactants at levels that are effective to achieve at least the directional effect of the cleaning operation. In connection with laundry detergents, these are:

117 “The levels of use” may vary widely, depending not only on the type and severity of soils and stains, but also on the temperature of the wash water, the volume of wash water and the type of washing machine. For example, top-loading washing machines, automatic US axial-axis types using from 45 to 83 liters of water per wash, a wash cycle of about 10 to 14 min, and a wash temperature of about 10 ° C to 50 ° C. In such scrubbers, use of from about 2 ppm to about 625 ppm, more preferably from 2 ppm to about 550 ppm, more preferably from 10 ppm to about 325 ppm of surfactant in the wash solution is preferred. Based on a utility dose of from 50 ml to about 150 ml per fill, this is transferred to a surfactant concentration in the product of from 0.1% to about 40%, preferably from 0.1% to about 35%, more preferably from 0% to 0%. , 5% to 15% for high performance liquid laundry detergents. Based on a user dose of from 30 g to about 950 g per fill, this represents a surfactant concentration in the product (by weight) of from 0.1% to about 50%, preferably from 0.1% to about 35%, for compact granular laundry detergent compositions. % and more preferably from 0.5% to about 15%. Based on utility dosages of from 80 g to about 100 g per fill, this for spray-dried granules (i.e., flake, with a density below about 650 g / l) represents a surfactant concentration in the product of from 0.07% to about 35%, preferably from 0.07 to about 25%, and more preferably from about 0.35% to about 11%.

For example, in European front-load and horizontal-axis automatic washing machines using from about 8 to 15 liters of water in a single wash cycle, a wash cycle of 10 to about 60 min and a wash water temperature of 30 ° C to about 95 ° C 3 ppm to about 14000 ppm, preferably from 3 ppm to about 10000 ppm, more preferably from 15 ppm to about 4200 ppm of surfactant in the wash solution. Based on a utility dose of from 45 ml to about 270 ml per fill, this is transferred to a surfactant concentration (by weight) in the product of from 0.1% to about 50%, preferably from 0.1% to about 35%, more preferably from 0%. , 5% to about 15% for high performance liquid laundry detergents. Based on a user dose of from about 40 grams to about 210 grams per fill, this represents a surfactant concentration in the product (by weight) of from about 0.12% to about 53%, for compact granules (density greater than 650 g / L) for washing. preferably from 0.12% to about 46% and more preferably from 0.6% to about 20%. Based on utility dosages of from 140 g to about 400 g per fill, this for spray dried granules (i.e., flake, with a density below about 650 g / l) represents a surfactant concentration in the product of from 0.03% to about 34%, preferably from 0.03 to about 24%, and more preferably from about 0.15% to about 10%. ,

For example, top-loading washers, automatic Japanese axial-axis types using from 26 to 52 liters of water per wash, washing cycle from about 8 to 15 min, and washing temperatures from about 5 ° C to 25 ° C. For these washing machines, use of from about 0.67 ppm to about 270 * is preferred.

ppm, more preferably from 0.67 ppm to about 236 ppm, even more preferably from 3.4 ppm to about 100 ppm of surfactant in the wash solution. Based on a utility dose of from 20 ml to about 30 ml per fill, this is transferred to a surfactant concentration (by weight) in the product of from 0.1% to about 40%, preferably from 0.1% to about 35%, more preferably from 0%. , 5% to about 15% for high performance liquid laundry detergents. Based on a user dose of from 18 g to about 35 g per fill, this represents, for compact (density greater than 650 g / l) granular laundry detergent compositions, a surfactant concentration in the product (by weight) of from 0.1% to about 50%, with preferably from 0.1% to about 35%, and more preferably from 0.5% to about 15%. Based on utility dosages of from 30 g to about 40 g per fill, this in spray dried granules (i.e., flake, with a density below about 650 g / l) represents a surfactant concentration in the product of from 0.06% to about 44%, preferably from 0.06 to about 30%, and more preferably from about 0.3% to about 13%.

As can be seen from the foregoing, the amount of surfactant used for automatic laundry washing may vary depending on the user's habits and practices, the type of washing machine, and the like.

In a preferred aspect of the use according to the invention, a dispersing device is used in the wash. The dispersing device is filled with a detergent product and is used to introduce the product directly into the drum of the washing machine before starting the washing cycle. Its bulk capacity should be such that it is able to accommodate a sufficient amount of the detergent product that would normally be used for washing.

Once the washing machine has been filled with laundry, the detergent dispersing device is placed inside the drum of the washing machine. At the beginning of the washing cycle of the washing machine, water is introduced into the drum and the drum starts to rotate periodically. The shape of the dispersing device should be such as to allow the dry detergent product to close, but then allow it to be released during the wash cycle depending on its mixing by the rotating drum and also as a result of its contact with the wash water.

In order to release the detergent product during washing, the device may comprise a plurality of openings through which the product may pass. Alternatively, the device may be made of a liquid permeable material, but impermeable to the solid product, allowing release of the dissolved product. Preferably, the detergent product will be released rapidly at the beginning of the wash cycle, thereby achieving temporarily high local product concentrations in the drum of the washing machine at this stage of the wash cycle.

• · · · · · · · · · · · · · · · · · · · ·

Preferred dispersing devices are reusable and are designed to maintain container integrity in both dry and wet conditions during the wash cycle. Particularly preferred are dispersing devices for use with the formulations described in the following patents: GB-B-2,157,717, GB-B-2,157,718, EP-A-0201376, EP-A-0288345 and EP-A-0288346. An article by J. Bland, published in Manufacturing Chemist, November 1989, pp. 41-46, also describes a dispersing device for use with granular laundry products of the type commonly known as "granulette". Other preferred dispersing devices for use with the compositions of this invention are described in PCT Patent Application WO94 / 11562.

Particularly preferred dispersing devices are described in European Patent Applications 0343069 and 0343070. The latter describes a device comprising a flexible pouch in the form of a bag that extends from a support ring defining an opening, the opening being made so that the bag permits a sufficient amount of product during one wash cycle in the wash process. A flow of washing medium flowing through the opening into the sachet dissolves the product and the solution then passes out through the opening into the washing medium. The support ring is equipped with a masking device to prevent leakage of wet, undissolved product. This arrangement typically includes radially elongated walls of a central, boss in the form of a circle or the like, where the walls have a helical structure.

Alternatively, the dispersing device may be a flexible container such as a bag or pocket. The bag may be of fibrous construction coated with a water impermeable material so as to retain the contents as described in European patent application 0018678. Alternatively, it may be formed of a synthetic water-insoluble material, provided that the stitched skirt or closure is designed so that The aqueous medium bursts as described in European Patent Applications 0011500, 0011501, 0011502 and 0011968. A convenient form of water-soluble sealed device comprises a water-soluble adhesive laid around the skirts and forming a pocket formed of an impermeable polymer film such as polyethylene or polypropylene.

Methods of automatic dishwashing

Any methods of automatic dish washing or cleaning of soiled dishes, especially soiled silver dishes, are contemplated.

Preferred methods of automatic dishwashing include treating soiled dishes, selected from earthenware, glass, hollow, silverware and cutlery, and mixtures thereof, with an aqueous liquid in which an effective amount is dissolved or dispersed.

120

of the automatic dishwashing composition of the present invention. An effective amount of an automatic dishwashing composition is from about 8 g to about 60 g of product dissolved or dispersed in a wash solution in a volume of from 3 to 10 liters, which are typical product doses and wash solution volumes commonly used in conventional automatic dishwashing machines.

Packaging of preparations

Commercially available bleach pads can be packaged in any suitable package, including those constructed from paper, paperboard, plastic materials, and other suitable laminates. A preferred package is described in European application 94921505.7.

Auxiliary rinsing aids and methods

The present invention also relates to compositions useful in the rinse cycle of the automatic dishwashing process, these compositions are commonly referred to as "auxiliary rinsers". While the above compositions may also be formulated for use as rinse aid, for use as a rinse aid, the compositions are not required to have a source of hydrogen peroxide present in such compositions (although a source of hydrogen peroxide is preferred, at least low concentrations to provide admixture).

The possible inclusion of a hydrogen peroxide source in the rinse means is possible in light of the fact that a significant degree of residual detergent composition is transferred from the wash cycle to the rinse cycle. Thus, when an ADD formulation containing a hydrogen peroxide source is used, the source is transferred from the wash to the rinse cycle. Thus, the catalytic activity provided by the bleach activator catalyst is effective with this transfer from the wash cycle.

Accordingly, the present invention further includes automatic dishwashing aids comprising: (a) an effective amount of a bleach activator and / or an organic peroxycarboxylic acid, (b) a catalytically effective knife of the catalyst described herein, and (c) an additional automatic dishwashing detergent material. . Preferred formulations comprise a low foaming nonionic surfactant. These compositions are also preferred in liquid or solid form.

The present invention also encompasses methods of washing tableware in domestic automatic dishwashers, said methods comprising working solid items during a washing operation.

121

an aqueous alkaline bath dishwasher cycle comprising the composition of the invention.

DETAILED DESCRIPTION OF THE INVENTION

In the following Examples, the abbreviations for the various ingredients used to prepare the compositions have the following meanings.

LAS: sodium salt of a linear C12 alkylbenzene sulfonate

C45AS: C14-C15 sodium linear alkyl sulfate

CxyEzS: Sodium C _x -C _y alkyl sulfate, branched condensed with z moles of ethylene oxide

CxyEz: C 1 _x -C 1 _y branched primary alcohol condensed on average with mole of ethylene oxide

QAS: R ₂ N ⁺ (CH 3) 2 (C ₂ H ₄ OH) with R ₂ = C, ₂ - C, ₄

TFAA. : C 16 -C 18 alkyl N-methylglucamide

STPP: anhydrous sodium tripolyphosphate

ZEOLIT A: hydrated sodium aluminosilicate of formula Nai2 (AlO2SiO2) i2.27H2O having a primary particle size ranging from 0.1 to 10 pm

NaSKS-6: Crystalline layered silicate of formula 5-Na2Si2O5

Carbonate: Anhydrous sodium carbonate with particle size between 200 µm and 900 µm

Bicarbonate: anhydrous sodium bicarbonate with particle size between 400 µm and 1200 µm

Silicate: Amorphous sodium silicate (SiO2: Na2O, 2.0 ratio)

Sodium sulphate: anhydrous sodium sulphate

Citrate: trisodium citrate dihydrate with an activity of 86.4% with a particle size distribution between 425 µm and 850 µm

MA / AA: 1: 4 myleinic / acrylic acid copolymer, average molecular weight about 70000.

CMC: Sodium carboxymethylcellulose protease: 4KNPU / g proteolytic enzyme produced by NOVO Industries A / S under the name Savinase

Cellulase: 1000 CEVU / g cellytic enzyme produced by NOVO Industries A / S under the name Carezym

Amylase: An amylolytic enzyme with an activity of 60 KNU / g sold by NOVO Industries A / S under <RTIgt;

Trademark Termamyl 60T Lipasa Lipolytic enzyme activity of 100kLU / g sold by NOVO Industries A / S under the trade name Lipolase PB4 : sodium perborate tetrahydrate of the nominal formula NaBO2.3H2O.H2O2 PB1 Anhydrous sodium perborate reagent of the nominal formula NaBO2.H2O2 Percarbonate : sodium percarbonate of the nominal formula 2Na2CO3.3H2O2 NaDCC : sodium dichloroisocyanurate NOBS Nonanoyloxybenzenesulfonate in the form of the anhydrous sodium salt DTPMP : diethylenetrieminpenta (methylene phosphonate), sold by Monsanto under the trade name called Dequest 2060

Photoactivated: sulfonated zinc phthalocyanine encapsulated in dextrin soluble polymer bleach

Brightener 1 : disodium 4,4´-bis (2-sulfostyryl) biphenyl Brightener 2 : 4,4'-bis (4-anilino-6-morpholino-1,3,5-triazin-2-yl) amino) stilbene-2,2'- disulfonate HEDP : 1,1-hydroxyethane diphosphonic acid CFP 1 : sulfobenzoyl-terminated ester with oxyethyleneoxy and terephthaloyl backbone Silicone Polydimethylsiloxane antifoam with siloxane-oxyalkylene antifoam agent copolymer as a dispersant with an anti-foam ratio and a dispersing agent of from 10: 1 to 100: 1. DTPA : diethylenetriaminepentaacetic acid

In the following Examples, all concentrations are expressed by weight of the formulation. The following examples are intended to illustrate the invention and are not intended to limit or otherwise limit the scope of the invention. All parts, percentages and ratios used in these examples are by weight unless otherwise indicated.

• ·

123 j ·

Example 1

The following laundry detergent compositions A-F were prepared as follows:

Ingredients AND (B) C D E F G Base-based bleach catalyst transition metal (1) 0.1 0.5 1.0 2,0 10.0 2,0 1.0 Detergent (1) 5000 4000 1000 ' 6000 5000 500 600 Primary oxidant (3) 1200 500 200 1200 1200 50 30 TAED (3) 200 100 ALIGN! 0 300 200 0 0 C8-14 bleach activator (5) 0 300 100 ALIGN! 50 100 ALIGN! 20 May 30 Chelating agent (6) 10 30 5 10 10 0 3

wherein the quantities are given as weights, e.g. kg or ppm.

(1) is a catalyst according to any of the foregoing syntheses, eg Synthetic Example 1 (2) a commercial detergent granule, e.g. TIDE or ARIEL, having no bleach or transition metal catalyst, or another conventional detergent powder, e.g. sodium carbonate and / or zeolite A or P (3) sodium perborate monohydrate or sodium perborate tetrahydrate or sodium percarbonate, (4) is tetraacetylethylenediamine or any equivalent polyacetylethylenediamine, such as an unsymmetrical derivative.

(5) is any hydrophobic bleach activator having a carbon chain length within the indicated range, eg, NOBS (C9) or NAPAA producing activator after perhydrolysis (C9); (6) is a commercial phosphonate chelant, eg, DTPA or one of the DEQUEST series; sodium salt of S, S-ethylenediamine disuccinate.

Preparations used for washing of laundry in household automatic washing machines USA, Europe and

Japan at a water hardness in the range of 0-20 gpg (grit per US gallon) and wash water temperatures from the cold range (room temperature) to 90 ° C, more typically from room temperature to about 60 ° C. The tabulated amounts may be read in any acceptable weight units, eg kilograms, for formulation purposes or, in the case of a single wash, in units of ppm in the wash solution. The washing pH is generally in the range of from 8 to about 10, depending on the product used for washing and the degree of soiling. Excellent results are obtained with various soiled items (nine reps for each item), such as t-shirts soiled with grass, tea, wine, pom-poms »·

124 · · šť šť šť 124,,,, ávy,,,,,,,,,, sauces, beta-carotene or carrots. The evaluation was carried out using five trained assessors, a group of 60 consumers or using tools such as a spectrometer.

Example 2

G-M Laundry Detergents are in accordance with the present invention:

Ingredients G H AND J TO L M Mn (Bcyclam) Cl2 0.05 0.02 0.005 0.1 0.05 0.001 2,0 PB4 10.0 9.0 9.0 - 8.0 12.0 12.0 PB1 10.0 - - 1.0 - - - Percarbonate - - 1.0 10.0 4.0 - - TAED - 1.5 2,0 5.0 1.0 1.5 1.5 NOBS 5.0 0.0 0.0 0.5 0.1 - - DETMP - 0.3 0.3 0.1 0.2 0.5 0.5 HEDP 0.5 0.3 0.3 0.3 0.1 0.3 0.3 DTPA 0.5 - - 0.1 - - - C11-C13LAS 20.0 8.0 7.0 8.0 - 8.0 12.0 C25E3 or C23E7 2,0 3.0 4.0 3.0 7.0 3.0 3.0 QAS - - - - - 1.0 2,0 STPP - - - - - - 30.0 Zeolite A 20.0 - 25.0 19.0 18.0 10.0 - For carbonate 20.0 20.0 13.0 30.0 25.0 27.0 10.0 Silicate 1-3 y. - 1.5 2,0 3.0 3.0 3.0 5.0 Protease 0.2 0.3 0.3 0.3 0.3 - - Amylase - 0.1 0.1. - 0.1 0.1 - Carezym 0.2 - 0.1 - - - - MA / AA or Na-polyacrylate 5.0 0.5 0.3 0.3 0.3 0.3 1.0 CMC - 0.2 0.2 0.2 0.2 0.2 0.2 sulfonated Zn- or Si phthalocyanine - 15 ppm - 20 ppp - 10 ppm 5 ppm Dirt-releasing polymer 0.2 - 0.5 0.2 1.0 - - Brightener 1 0.2 0.1 0.1 0.1 0.1 0.1 0.1

• · • ·

125 · · · · · · · · · · · · · · · · · · · · · ·

Perfume 0.2 0.3 - 0.3 0.3 0.3 0.3 silicone antifoam 0.2 0.4 0.5 0.3 0.5 0.5 - PEG 1.0 - 1.0. - - - - Humidity 7.0 6.0 5.0 8.0 7.0 7.0 9.0 Sodium and minority sulphate: up to 100% 100% 100% 100% 100% 100% 100% Density (g / 1) 500 800 750 850 850 850 650

The formulations are used for textile washing as in the above example. In addition, the pads, except for G, can be used for soaking and handwashing fabrics with excellent performance.

Example 3

The following N-T granular laundry compositions are prepared in accordance with the present invention:

Ingredients N O P Q R WITH T Mn (Bcyclam) Cl2 0.01 0.02 0.005 0.1 0.05 0.001 2,0 PB4 5.0 9.0 9.0 - 8.0 12.0 12.0 PB1 - - - 1.0 - - - Percarbonate - - 1.0 10.0 4.0 - - TAED. - 1.5 2,0 5.0 1.0 1.5 1.5 NOBS 4.0 0.0 0.0 0.5 0.1 - - DETMP - 0.3 0.3 0.1 0.2 0.5 0.5 HEDP - 0.3 0.3 · 0.3 0.1 0.3 0.3 DTPA 0.3 - - 0.1 - - - C11-C13LAS 5.0 8.0 7.0 8.0 - 8.0 12.0 C25E3 or C45E7 3.2 3.0 4.0 3.0 7.0 3.0 3.0 QAS - - - - - 1.0 2,0 STPP - - - - - - 30.0 Zeolite A 10.0 - 15.0 19.0 18.0 10.0 - For carbonate 6.0 10.0 20.0 30.0 25.0 27.0 10.0 Silicate 1-3 y. 7.0 1.5 2,0 3.0 3.0 3.0 5.0

126 • »« *.. · · · · · · · ·

Na-SKS-6 - 5.0 10.0 - - - - Protease 0.3 0.3 0.3 0.3 0.3 - - Amylase 0.1 0.1 0.1 - 0.1 0.1 - Lipase 0.1 - 0.1 - - - - MA / AA or Na-polyacrylate 0.8 0.5 0.3 0.3 0.3 0.3 1.0 CMC 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Ca-montmorillonite - - - 5.0 - - - Dirt-Releasing Polymer ” 0.2 - 0.5 0.2 1.0 - - Brightener 1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Perfume' 0.2 0.3 - 0.3 0.3 0.3 0.3 silicone antifoam 0.2 0.4 0.5 0.3 0.5 0.5 - Humidity 7.0 6.0 5.0 8.0 7.0 7.0 9.0 Sodium and minority sulphate: up to 100% 100% 100% 100% 100% 100% 100% Density (g / 1) 500 800 750 850 850 850 650

The compositions are used to wash textiles as well as the above examples.

Example 4

The following detergent compositions are in accordance with the present invention:

Ingredients AT IN W X bleach catalyst * 0.02 0.05 0.1 1.0 PB1 6.0 2,0 5.0 3.0 NOBS 2,0 1.0 3.0 2,0 LAS 15.0 14.0 14.0 18.0 C45AS 2.7 1.0 3.0 6.0 TFAA - 1.0 - - C25E3 or C45E7 - 2,0 - 0.5 C45E3S - 2.5 - - Zeolite A 30.0 18.0 30.0 22.0 Carbonate 13.0 7.5 - 5.0 Silicate 9.0 5.0 10.0 8.0

127 fc

Bicarbonate - 7.5 - - DTPMP 0.7 1.0 - - CFP 1 0.3 0.2 - 0.1 MA / AA 2,0 1.5 2,0 1.0 CMC 0.8 0.4 0.4 0.2 Protease 0.8 1.0 0.5 0.5 Amylase 0.8 0.4 - 0.25 Lipase 0.2 0.1 0.2 0.1 Cellulose 0.1 0.05 - - Brightener 1 0.2 0.2 0.08 0.2 Polyethylene oxide with molecular weight mass 5 000 000 - 0.2 - 0.2 Bentonite clay - - - 10.0 Refill (humidity and various) 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN!

* Mn (Bcyclam) Cl2 according to Synthetic Example 1 or Synthetic Examples 2-7.

Example 5

The following high-density detergent compositions are in accordance with the present invention:

Agglomerate ¥ OF C45AS 11.0 14.0 LAS 3.0 3.0 Zeolite A 15.0 10.0 Carbonate 4.0 8.0 MA / AA 4.0 2,0 CMC 0.5 0.5 DTPMP 0.4 0.4 Spray ováný C25E5 5.0 5.0 Perfume 0.5 0.5 Added dry

128

LAS 6.0 3.0 HEDP 0.5 0.3 SKS-6 13.0 6.0 Citrate 3.0 1.0 TAED 5.0 7.0 Percarbonate 20.0 20.0 Bleach catalyst * 0.5 0.1 CFP 1 0.3 0.3 Protease 1.4 1.4 Lipase 0.4 0.4 Cellulose 0.6 0.6 Amylase 0.6 0.6 Silicone antifoam 5.0 5.0 Brightener 1 0.2 0.2 Brightener 2 0.2 - Refill (humidity and various) 100 ALIGN! 100 ALIGN! Density (g / 1) 850 850

Bě Mn Bleach Catalyst (Bcyclam) Cl2 according to Synthesis Examples 1 above, benefits are also observed for formulations having a bleach catalyst according to Synthetic Example 2-7.

Example 6

An example (non-limiting) non-aqueous bleach-containing liquid laundry detergent composition is prepared according to the composition in Table I.

Table I Component Weight % Range (% w / w) Liquid phase C12 Linear alkylbenzene sulfonate (LAS) 25.3 18-35 C12.14, EO5 alcohol ethoxylate 13.6 10-20 Hexylene glycol 27.3 20-30

129

Perfume

Solids protease enzyme

For ₃ citrate, anhydrous

Bleach catalyst *

Natrium perborate

Sodium nonanoyloxybenzenesulfonate (NOBS) Sodium carbonate

Diethyltriaminepentaacetic acid (DTPA)

Brightener antifoam agent

Minority

9 · · • · · 0.4 • · »··« » 0-1.0 0.4 0-1.0 4.3 3-6 2.5 10 3.4 2-7 8.0 2-12 13.9 5-20 0.9 0-1,5 0.4 0-0.6 0.1 0-0.3 fill in

The bleach catalyst Mn (Bcyklam) Cl2 according to Synthetic Example 1 of the above-mentioned drive, the benefits are also observable for compositions having the bleach catalyst according to Synthetic Example 2-7.

The resulting compositions are stable, anhydrous, highly active laundry detergent compositions, providing excellent stain and dirt removal performance in use during normal fabric washing.

Example 7

The following examples further illustrate the invention with respect to granular automatic dishwashing detergents containing phosphates.

% by weight of active material

Ingredients . AND (B) STPP (anhydrous) ¹ 31 26 Sodium carbonate 22nd 32 Silicate (ratio 2, hydrated) 9 7 Surfactant (nonionic, eg Plurafac, BASF) 3 1.5 Bleach catalyst ² 0.01 0.1 Natrium perborate 12 10 TAED 1.0 1.5

• ·

130

Savinase - 0.2

Termamyl 0,5

Sulfate 25 25

Perfume / Minorities up to 100% to 100% Sodium Tripolyphosphates

The bleach catalyst Mn (Bcyclam) Cl2 according to Synthetic Example 1 above, the benefits are also observable for compositions having the bleach catalyst according to Synthetic Example 2-7.

Example 8

In the following example, an automatic dishwashing detergent is provided illustrating the combination of the transition metal catalyst of any one of Synthetic Examples 1-7 with an inorganic peracid, sodium monopersulfate.

% by weight of active material Ingredients AND (B) STPP (anhydrous) ¹ 31 26 Sodium carbonate 22nd 32 OXONE monopersulfate • 5 10 Surfactant (nonionic, eg Plurafac, BASF) 3 1.5 Bleach catalyst ² 0.01 0.1 Natrium perborate 12 1 TAED 2,0 1.5 Savinase - 0.2 Termamyl 0.5 Sulphate 25 25 Perfume / minorities up to 100% up to 100% 'Sodium tripolyphosphate

Example 9

The transition metal catalyst of Synthetic Example 1 and magnesium monoperoxyphthalate hexahydrate (0.05% / 10%) were added to an otherwise conventional soaking / hand washing product.

• ·

131

Example 10

The transition metal catalyst of Synthetic Example 1 in the form of a dilute aqueous solution was charged into the chamber of a two-chamber liquid dispersion bottle. The diluted stabilized peracetic acid solution was filled into a second chamber. The bottle was used to disperse the catalyst / peroxyacetic acid mixture as an additive into an otherwise conventional laundry wash in which no additional bleach was used.

Example 11

The transition metal catalyst of Synthetic Example 1 is used at pH 8 in combination with a low-foaming nonionic surfactant (Plurafac LF404), sodium carbonate, anionic dispersant (sodium polyacrylate, molecular weight 4000) and peroxyacetic acid in a glass cleaner and low plastics cleaner. pH. The cleaner can be used in institutional and domestic applications.

Example 12

A water-soluble plastic film bag containing a plurality of compartments separated by the sealed zones was filled with the following components:

A. Nonionic surfactant and colorant A (liquid or waxy phase)

B. Transition Metal Bleach Catalyst of Example 1 premixed with trisodium citrate as a work-diluent

C. Perfume

D. Brightener

E. sodium perborate monohydrate

F. 2,2-oxydisuccinate, sodium + sodium polyacrylate and colorant B

G. NOBS / S, S-EDDS premixed 1: 0.5 and colorant C

H. enzymatically hydrolyzable perfume (ester or acetal)

I. fabric care polymer

J. Protease / amylase enzyme

Ingredient concentrations may vary, however, include amounts common to Japanese wash conditions. The product is used in Japanese 'automatic washing machines operating at temperatures around 40 ° C to make the washed laundry more comfortable to wear and at the same time excellent »»

132 _:

bleaching, cleaning results and good care of laundry. The product is preferably pre-dissolved in warm water before being added to the scrubber.

Example 13

Synthesis of dithiocyanato manganese (H) 5,8-dimethyl-1,5,8,12-tetraazabicyclo [10.3.2] heptadecane

Synthesis of 1,5,9,13-tetraazatetracyclo [11.2.2.2 ^5,9 ] heptadecane

1.4.8.12- Tetraazacyclopentadecane (4.00 g, 18.7 mmol) was suspended in 30 mL acetonitrile under argon and glyoxal (3.00 g, 40% aqueous, 20.7 mmol) was added. The resulting mixture was heated at 65 ° C for 2 h. The acetonitrile was removed under reduced pressure. Distilled water (5 ml) was then added and the mixture was extracted with 5 x 40 ml chloroform. After drying over anhydrous sodium sulfate and filtration, the solvent was removed under reduced pressure. The product was then chromatographed on neutral alumina (15 x 2.5 cm) using chloroform / methanol (97.5: 2.5 increases to 95: 5). The solvent was removed under reduced pressure and the resulting oil was dried under vacuum overnight. Yield: 3.80 g of compound I (87%).

Synthesis of 1,3-Dimethyl-1,13-diazonium-5,9-tetraazatetracyclo [11.2.2.2 ^5,9 ] heptadecane diiodide

1.5.9.13- Tetraazatetracyklo [11.2.2.2 ^{5 '9]} heptadecane (5.50 g, 23.3 mmol) was dissolved in 180 ml of acetonitrile under a nitrogen atmosphere. Iodomethane (21.75 mL, 349.5 mmol) was then added and the reaction was stirred at room temperature for 10 days. The solution was rotary evaporated to give a dark brown oil. The oil was dissolved in absolute alcohol (100 mL) and the solution was refluxed for 1 h. During this time a gray colored solid formed which was separated from the mother liquor by vacuum filtration using Whatman # 1 filter paper. The solid was dried under vacuum overnight. Yield: 1.79 g, Π (15%). FAB mass spectrum (TG / G, MeOH) M + 266 m / z, 60%, Me 393 m / z, 25%.

Synthesis of 5,8-dimethyl-1,5,8,12-tetraazabicyclo [10.3.2] heptadecane

133 ...........

··· ·· · · · · ·

To a stirred solution of Π (1.78 g, 3.40 mmol) in ethanol (100 mL, 95%) was added sodium borohydride (3.78 g, 0.100 mmol). The reaction was stirred under nitrogen for 4 days at room temperature. 10% aqueous hydrochloric acid was then carefully added up to pH 1-2 to quench unreacted NaBEL}. Then 70 ml of ethanol were added. The solvent was removed on a rotary evaporator under reduced pressure, then the product was dissolved in aqueous KOH (125 mL, 20%) to give a solution of pH 14. The product was extracted with 5 x 60 mL of benzene and the combined organic layers were dried over anhydrous. sodium sulfate. After filtration, the solvent was evaporated under reduced pressure. The residue was stirred with crushed KOH and then distilled at 97 ° C and 1 mm pressure. Yield: 0.42 g, ΠΙ (47%). Mass spectrum (DCI / NH 3 / CH 2 Cl 2) MH ⁺ , 269 m / z, 100%.

Synthesis of dithiocyanato manganese (II) 5,8-dimethyl-1,5,8,12-tetraazabicyclo [10.3.2] heptadecane

Ligand ΙΠ (0.200 g, 0.750 mmol) was dissolved in 4.0 mL acetonitrile and manganese (II) dipyridine dichloride (0.213 g, 0.75 mmol) was added. The reaction was stirred at room temperature for 4 h to give a light golden solution. The solvent was removed under reduced pressure. A solution of sodium thiocyanate (0.162 g, 2.00 mmol) in 4 mL of methanol was then added. The reaction was heated for 15 min. The reaction solution was then filtered through a pad of celite and allowed to evaporate. The resulting crystals were washed with ethanol and dried under vacuum. Yield: 0.125 g, 38%. The solid contains NaCl so that it was recrystallized from acetonitrile to give 0.11 g of an off-white solid. Elemental analysis calculated:% C, 46.65,% H, 7.34,% N, 19.13. Found:% C, 45.70,% H, 7.10,% N, 19.00.

Industrial applicability

The invention relates to laundry or cleaning compositions comprising an effective amount of a bleach activator and / or an organic peroxyacid, a catalytically effective amount of a transition metal bleach catalyst, and another additive material, which is typically an oxygen bleaching agent. These compositions are suitable for all types of household automatic washing machines for washing laundry, as automatic dishwashing detergents, and as cleaning agents for cleaning hard surfaces, while providing better cleaning and bleaching effects than prior art compositions.

Claims (8)

PATENT CLAIMS (1) said transition metal is selected from the group consisting of Μη (Π), Μη (ΙΠ), Mn (IV), Mn (V), Fe (fi), Fe (ffl), Fe (IV), Co (I) Co (H), Co (III), Ni (I), Νι (Π), Ni (HI), Cu (II), Cu (II), Cu (m), Cr (II), Cr (in) , Cr (IV), Cr (VI), V (III), V (IV), V (V), Mo (IV), Mo (V), Mo (VI), W (IV) , W (V), W (VI), Pd (II), Ru (fi), Ru (m) and Ru (IV), and (2) said cross-bridged macropolycyclic ligand is selected from the group consisting of: (I) a cross-bridged macropolycyclic ligand of formula (I) having a dentition of 4 or 5: (ii) a cross-bridged macropolycyclic ligand of general formula (Π) having a denticity of 5 or 6: (Π) (iii) A cross-bridged macropolycyclic ligand of general formula (ΙΠ) having a dentition of 6 or 7: G. OF Zest /Ri / Λ / ¹ * G RnD M \ Ίχ / G \ (ΠΙ) D ' D E ^ZX Rn> Řn ', with the following formulas: - each E is a group (CR _n ) and X- (CR _n ) a ', wherein -X- is selected from the group consisting of O, S, NR and P, or is a covalent bond and preferably X is a covalent bond and for each E is the sum of a + and a 'independently selected from 1 to 5, more preferably 2 and 3; each G is a group (CR n) b; each R is independently selected from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl and heteroaryl, or two or more R covalently bonded to form an aromatic, heteroaromatic, cycloalkyl or heterocycloalkyl ring; each D is a donor atom independently selected from the group consisting of N, O, S and P, and at least two D atoms are cross-bridged donor atoms coordinated to the transition metal; - B is a carbon atom or a D donor atom or a cycloalkyl or heterocyclic ring; each n is an integer independently selected from 1 and 2, complementing the valency of the carbon atoms to which the R units are covalently attached; each n is an integer independently selected from 0 and 1, complementing the valency of the D donor atoms to which the R groups are covalently bonded; each n is an integer independently selected from 0, 1 and 2, complementing the valency of the B atoms to which the R units are covalently bonded; - each aaa 'is an integer independently selected from 0 to 5, preferably a + a' is 2 or 3, wherein the sum of all a plus a 'in the ligand of formula (I) ranges from about 8 to 12, the sum of all and plus a 'in the ligand of formula (Π) is in the range of 10 to 15 and the sum of all a plus a' in the ligand of formula (ΙΠ) is in the range of 12 to 18; each b is an integer independently selected from 0-9, preferably 0-5, or any one of the above formulas lacks one or more groups (CR n) b covalently bonded from any D to B if at least two (CR n) b covalently binds two D donor atoms to atom B in the formula and the sum of all b is from 1 to 5; and (iii) 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', SCIST, N ₃ ', CN', F ', ï, Br', Γ, O ₂ ', NO ₃ ', NO ₂ ', SO4 ² ', SO ₃ ² ', PO4 ³ ', organic phosphates, organic phosphonates, organic sulphates, organic sulfonates and aromatic N donors such as pyridines, pyrazines, pyrazole, imidazoles, benzimidazoles, pyrimidines, triazoles and thiazoles wherein R is H, optionally substituted alkyl, optionally substituted aryl, and (c) at least 0.1% of one or more laundry or scrubbing agents additional materials, preferably comprising oxygen bleaching agents. 139 «· ·« · ·· ·· (1) said transition metal is selected from the group consisting of Μη (Π), Μη (ΙΠ), Mn (IV), Mn (V), Fe (D), Fe (m), Fe (IV), and Co (I) , Co (II), Co (DI), Ni (I), Ni (D), Ni (ID), Cu (1), Cu (D), Cu (m), Cr (II), Cr (DI) , Cr (IV), Cr (VI), V (HI), V (IV), V (V), Mo (IV), Mo (V), Mo (VI), W (TV) , W (VI), W (VI), Pd (H), Ru (D), Ru (IH) and Ru (IV), preferably Μη (Π), Μη (ΙΠ), Mn (IV), Fe ( H), Fe (IV), Fe (IV), Cr (H), Cr (m), Cr (IV), Cr (V), and Cr (VI); 1. A detergent or cleaning composition comprising: (a) an effective amount, preferably from 0.0001% to 99.9%, more preferably from 0.1% to 25% of a bleach activator and / or an organic peroxycarboxylic acid, (b) a catalytically effective amount, preferably from 1 ppb to 99.9% transition metal bleach catalyst which is a transition metal complex and cross-bridged macropolycyclic ligand (c) addition to 100% of one or more laundry or cleaning additive materials, preferably comprising oxygen bleaching agents. (2) said cross-bridged macropolycyclic ligand is coordinated by four or five donor atoms to the same transition metal and includes: (i) 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 by covalent linkages of 3 or 3 non-donor atoms, wherein two to five (preferably three or four, more preferably four) of these donor atoms are coordinated in complex with the same transition metal atom; (ii) a cross-bridged chain covalently linking at least 2 non-adjacent organic macrocyclic ring donor atoms, said covalently The 135 non-adjacent donor atoms are cross-bridged donor atoms that are coordinated to the same transition metal in the complex and wherein said cross-bridged chains comprise from 2 to 10 atoms (preferably the cross-bridged chain is selected from 2, 3 or 4 non-donor atoms and 4). (Iii) 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 ', Ni, TIN, F, Cf, Br, Γ, O ₂ ', NO ₃ ', NO ₂ ', SO ₄ ² ', SO3 ² ', PO4 ³ ', organic phosphates, organic phosphonates, organic sulphates, 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, and (c) at least 0.1% of one or more of the works; cleaning p of extension materials, preferably consisting of oxygen bleaches. 2. A detergent or cleaning composition comprising: (a) an effective amount, preferably from 0.0001% to 99.9%, more preferably from 0.1% to 25% of a bleach activator and / or an organic peroxycarboxylic acid, (b) a catalytically effective amount, preferably from 1% to 49% transition metal bleach catalyst, said catalyst comprising a transition metal complex and cross-bridged macropolycyclic ligands, wherein: A laundry detergent or cleaning composition according to claims 1 and 2, wherein said activator is a hydrophobic bleach activator, preferably sodium nonanoyloxybenzenesulfonate or hydrophilic. a bleach activator such as Ν, Ν, ’,, tetraacetylethylenediamine. 4. A detergent or cleaning composition comprising: (a) an effective amount, preferably from 0.0001% to 99.9%, more preferably from 0.1% to 25% of a bleach activator and / or an organic peroxycarboxylic acid, (b) a catalytically effective amount, preferably from 1% to 49% transition metal bleach catalyst, said catalyst comprising a transition metal complex and a cross-bridged macropolycyclic ligand, wherein: Compositions or methods according to any one of claims 1 to 4, characterized in that they comprise an activator selected from the group comprising cationic bleach activators, preferably quaternary carbamate, quaternary carbonate, quaternary ester and quaternary amide types of cationic bleach activators, phenol sulfonate esters of alkanoylamino acids, acyl phenol sulfonates , acylalkylphenolsulfonates, acyloxybenzenesulfonates and bleach activators having the general formula: R1-N-C-R2-C-L R 5 and RC (O) -L or mixtures thereof, wherein R is a C 2 -C 18 saturated or unsaturated alkyl, aryl or alkylaryl group, R ¹ is an alkyl, aryl or alkaryl group containing from 1 to 14 carbon atoms, preferably R and R ¹ are particularly 8 to 12 carbon atoms, R ² is alkylene, arylene or alkarylene containing from 1 to 14 carbon atoms, ^R5 is H or alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L is a leaving group, preferably selected from the group consisting of: -O-CH = C-CH = CH ₂ -o-ch = c-ch = ch ₂ O ¹¹ 4 -OCR ¹ ch ₂ -c / \ CII o -NR Yθ / - ^c > - ^N - _c / II o NR ² R ³ I. Ό — C = CHR ⁴ , a OY II ¹ -N —S-CH —R ⁴ L 2 R ³ O 139 19 & -l <teS · fr fr fr »ψ ψ - ψ ψ» »» »» »» »a a» a a a a a mixtures thereof, wherein R ¹ is a linear or branched alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R ³ is an alkyl chain containing from 1 to 8 carbon atoms, ^R4 is H or ^R3, and Y is H or a dissolution facilitating group wherein preferred solubility enhancing groups are selected from the group consisting of -SOaTvf, -CO2'M'-SOfM ', -N + (R) 4X' and O <N (R ³ ) 2, more preferably -SO ³ -M ⁺ and -CO ₂ M ⁺ , wherein R ³ is an alkyl chain containing from 1 to 4 carbon atoms, M is a bleach-stable cation and X is a bleach-stable anion, and bleach activators of the formula: wherein R ⁶ is H, alkyl, aryl, alkoxyaryl, alkaryl of from 1 to 12 carbon atoms, or substituted phenyl of from 6 to 8 carbon atoms. A detergent or cleaning composition or process according to any one of claims 1 to 5 comprising a bleach activator selected from the group consisting of 2- (N, N, N-trimethylammonium) ethyl 4-sulfophenyl carbonate, N-octyl-N, N -dimethyl-N-10-carbophenoxydecylammonium chloride, 3- (N, N, N-trimethylammonium) propyl sodium 4-sulfophenylcarboxylate, Ν, Ν, Ν-trimethylammoniumtoluyloxybenzenesulfonate, Ν, Ν, Ν ', Ν'-tetraacetylethylenediene ethylene diene , sodium 4-benzyloxybenzenesulfonate, sodium 1-methyl-2-benzyloxybenzenesulfonate, sodium 4-methyl-3-benzyloxybenzoate, trimethylammoniumtoluyloxybenzenesulfonate, sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate, (6-octanamido-cocaproylbenzone), ) oxybenzenesulfonate and mixtures thereof. 7> / · 9 9 9 9 · ι ι ι ι ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft ft 9 9 9 9 9 9 9 9 phthaloylaminoperoxycaproic acid, 6-octylamino-6-oxoperoxyhexanoic acid, peroxyacetic acid, phthaloylimidoperoxycaproic acid and related arylimidosubstituted and acyloxy nitrogen derivatives, 12-diperoxydodecanedioic acid, 1,9-diperoxyazaleic acid, diperoxybrassilic acid, diperoxysebacic acid, diperoxyisophthalic acid, 2-decyldiperoxybutane-1,4-dioic acid, 4,4'-sulfonylbisperoxybenzoic acid and their salts. A detergent or cleaning composition or process according to any one of claims 1 to 6, characterized in that it comprises an organic peroxycarboxylic acid selected from the group consisting of magnesium monoperoxyphthalate hexahydrate, m-chloroperbenzoic acid, 4-nonylamino-4-oxopeoxybutyric acid, 6-nonylamino- 6-oxoperoxycaproic acid, peroxybenzoic acid and ring-substituted peroxybenzoic acids preferably peroxy-α-naphthoic acid, aliphatic, substituted aliphatic and arylalkylmonoperoxy acids, preferably peroxylauric acid, peroxystearic acid, N, N140 8. A detergent or cleaning composition comprising: (a) an effective amount, preferably from 1 ppm to 99.9%, more preferably from 0.1% to 25% of the bleach activator, (b) a catalytically effective amount, preferably from 1 ppb to 99.9%, more preferably from 0.001 ppm to 49%, more preferably from 0.05 ppm to 500 ppm of a transition metal bleach catalyst, said catalyst comprising a 1: 1 catalytic manganese complex selected from the group consisting of Μη (Π), Μη (ΠΓ), Mn (IV) and tetradentate cross-bridged macropolycyclic ligand of general formula: wherein R ¹ is independently selected from H and linear or branched, substituted or unsubstituted C 1 -C 20 alkyl, alkenyl or alkynyl, and preferably all nitrogen atoms in the macropolycyclic rings are coordinated to the transition metal and optionally one or more non-polycyclic ligands (c) 100%, preferably at least 0.1%, of one or more additional cleaning or laundry materials, comprising oxygen bleaching agents preferably selected from the group consisting of hydrogen peroxide, perborate and percarbonate.