DE69827738T2 - bleach activation - Google Patents

Description

Field of the invention

The This invention relates to the activation of bleaching agents which Including peroxy compounds Hydrogen peroxide or hydrogen peroxide adducts, the hydrogen peroxide in watery solution release, and peroxyacids (or precursor use thereof); on compounds that activate peroxy compounds or catalyze; on bleaching compositions, including wash bleach compositions, which is a catalyst for Containing peroxy compounds; and to processes for bleaching and / or Washing substrates using the aforementioned compositions.

Especially The present invention relates to the new use of iron compounds as catalysts for the bleach activation of peroxy compounds.

background the invention

peroxide bleaching agent for use in washing have been known for many years. These Means are used to remove stains such as tea, fruit and wine stains, from garments effective at or near boiling temperatures. The effectiveness of peroxide bleaches leaves at temperatures below 60 ° C strong after.

Previous Patent applications deal with environmentally friendly manganese ions and complexes. US-A-4,728,455 explained the use of Mn (III) gluconate as a peroxide bleach catalyst with high hydrolytic and oxidative stability; however, will be relatively high conditions from ligand (gluconate) to Mn needed, to the desired to obtain catalytic system. Besides, the performance of this is Mn-based catalysts insufficient when bleaching be used in low temperature ranges of about 20 to 40 ° C, and they are effective in removing a wide range restricted to spots.

In several patent documents, for example EP-A-458,379, are new Triazacyclononane-based manganese complexes which have a high catalytic oxidation activity at low temperatures, which is particularly suitable for bleaching purposes is. A major improvement in bleaching activity could be obtained by the fact be that these Compounds under washing conditions, for example, high alkalinity and oxidizing Environment (due to the presence of hydrogen peroxide or peroxyacids), stable are.

In addition to the above mentioned Stain removal is the color transfer a well-known problem in the art and is in different Because of being addressed. For example, an improved color transfer inhibition through the use of Fe-porphyrin and Fe-phthalocyanine complexes (see EP-A-537,381, EP-A-553,607, EP-A-538,228).

It It is well known that the stability of Fe coordination complexes in alkaline, aqueous media in the presence of peroxide compounds is very bad. In EP-A-537,381 and EP-A-553,607 there are disclosed methods of improvement in this regard.

These bad stability led by Fe coordination species on the need for very low concentrations of peroxide and also for the use of polymers (see EP-A-538,228). These measures reduce only the negative effects of the above bad stability In some way and do not complete solution for this Problem ready.

In WO-A-9534628 has been shown that the use of iron compounds, the five-fold nitrogen-containing In particular the use of N, N-bis (pyridin-2-ylmethyl) -bis (pyridin-2-yl) methylamine, as bleaching and oxidation catalysts at a favorable Bleaching activity, dye bleaching activity and oxidation activity in general led.

We found surprising out that one significantly improved catalytic oxidation activity of the Fe coordination complex by substituting the H atom of the C-H group of the methylamine component, the in the ligands according to WO-A-9534628 can be obtained by other groups.

As a result, these new iron compounds have been found to provide convenient stain removal in the presence of hydrogen peroxide or peroxyacids. It is also an improved Bleaching activity in alkaline aqueous solutions containing peroxy compounds at concentrations generally present in scrubbing liquid during the fabric washing cycle is particularly noted.

In addition, show These new iron compounds have remarkable properties in terms of the dye transfer inhibition and alternatively the oxidation of organic substances, such as olefins, Alcohols and non-activated hydrocarbons.

Definition of the invention

worin R₁ C₀-C₂₀-Alkylaryl, C₀-C₂₀-Alkylheteroaryl, C₀-C₂₀-Alkyl darstellt, mit der Maßgabe, daß R₁ nicht Wasserstoff darstellt, und R₂, R₃, R₄, R₅ unabhängig voneinander aus C₀-C₅-Alkyl, substituiert mit einem Pyridinring, ausgewählt sind.In one aspect, the present invention provides a bleach and oxidation catalyst comprising an Fe complex having the formula (A): [LFeX _n] ^z Y _q (A) or precursors thereof, wherein
Fe is iron in the oxidation number II, III, IV or V;
X represents a coordinating species is such as H ₂ O, ROH, NR _3, RCN, OH ^-, OOH, RS ^-, RO ^-, RCOO ^-, OCN ^-, SCN ^-, N ₃ ^-, CN ^-, F ^-, Cl ^- , Br ^-, I ^-, O ^2-, NO ₃ ^-, NO ₂ ^-, SO ₄ ^2-, SO ₃ ^2-, PO ₄ ^3- or aromatic N donors such as pyridines, pyrazines, pyrazoles, Imidazle, benzimidazoles, Pyrimidines, triazoles and thiazoles, wherein R is H, optionally substituted alkyl or optionally substituted aryl;
n is an integer between 0 and 3;
Y is a counterion, the type of which depends on the charge of the complex;
q = z / [charge Y];
z indicates the charge of the complex and is an integer that may be positive, zero or negative; when Y z is positive, is an anion such as F ^-, Cl ^-, Br ^-, I ^-, NO ₃ ^-, BPh ₄ ^-, ClO ₄ ^-, BF ₄ ^-, PF ₆ ^-, RSO ₃ ^-, RSO ₄ ^-, SO _{4 is} ^2- , CF ₃ SO ₃ ^- or RCOO ^- ; when z is negative, Y is a common cation such as an alkali metal, alkaline earth metal or (alkyl) ammonium cation;
L represents a ligand of the general formula (B):

wherein R _{1 is} C ₀ -C ₂₀ -alkylaryl, C ₀ -C ₂₀ -alkyl heteroaryl, C ₀ -C ₂₀ -alkyl, with the proviso that R _{1 is} not hydrogen, and R ₂ , R ₃ , R ₄ , R _{5 are} independently selected from C ₀ -C ₅ alkyl substituted with a pyridine ring.

In In another aspect, the present invention provides a bleaching composition, comprising a peroxy bleach compound, preferably selected from Hydrogen peroxide, hydrogen peroxide releasing or generating Compounds, peroxyacid and their salts and mixtures thereof, optionally together with Peroxysäurebleichpräkursorn, and a catalyst according to the present invention Invention ready.

Detailed description of the invention

in the In general, the Fe complex catalyst according to the invention in a bleach system comprising a peroxy compound or a precursor thereof comprises can be used, and for use in washing and bleaching of substrates, including To make the laundry, Wash the dishes and cleaning hard surfaces be suitable. Alternatively, the Fe complex catalyst according to the invention for Bleaching of textile, paper and pulp products as well be used in wastewater treatment.

As already mentioned, is an advantage of the Fe complex catalysts according to the invention that she in the presence of peroxy compounds a remarkably high oxidation activity in alkaline watery media deliver.

A second advantage of the new Fe complex catalysts of the present invention is that they exhibit good bleaching activity over a broader pH range (generally pH 6 to 11) than has been observed for the iron complexes disclosed so far. Their performance was especially at a pH of 10 ver repaired. This benefit may be particularly useful in view of current cleansing formulations that tend to use alkaline conditions, as well as the propensity to shift the pH from alkaline (usually a pH of 10) during the fabric wash to more neutral levels. Furthermore, this advantage may be useful when the particular iron complex catalyst is used in dishwashing formulations.

One additional The advantage is that the Compounds as dye transfer inhibiting agents are effective as shown in Example 5.

One Another advantage is that the catalysts of the invention have a relatively low molecular weight and therefore very are weight-effective.

Precursors of the active Fe complex catalysts of this invention may be any iron coordination complex which is converted to the active iron complex of general formula (A) under fabric washing conditions. Alternatively, the precursor of the Fe complex of the invention may be a mixture of an iron salt, such as Fe (NO ₃ ) ₃ , and the ligand L.

The class of ligands is that of compounds of general formula (B) wherein the substituent group R _{1 is selected} from C ₀ -C ₂₀ -alkylaryl, C ₀ -C ₂₀ -alkyl heteroaryl and C ₀ -C ₂₀ -alkyl, and wherein the Substituent groups R ₂ , R ₃ , R ₄ and R _{5 are} independently selected from C ₀ -C ₅ alkyl substituted with a pyridine ring, and R _{1 is} other than H.

Examples of preferred ligands in their simplest forms are:
N, N-bis (pyridin-2-yl-methyl) -1,1-bis (pyridin-2-yl) -1-aminoethane;
N, N-bis (pyridin-2-yl-methyl) -1,1-bis (pyridin-2-yl) -2-phenyl-1-aminoethane;
N, N-bis (imidazol-2-yl-methyl) -1,1-bis (pyridin-2-yl) -1-aminoethane.

More preferred ligands are:
N, N-bis (pyridin-2-yl-methyl) -1,1-bis (pyridin-2-yl) -1-aminoethane;
N, N-bis (pyridin-2-yl-methyl) -1,1-bis (pyridin-2-yl) -1-aminohexane;
N, N-bis (pyridin-2-yl-methyl) -1,1-bis (pyridin-2-yl) -2-phenyl-1-aminoethane;
N, N-bis (pyridin-2-yl-methyl) -1,1-bis (pyridin-2-yl) -2- (4-sulfonfsäure-phenyl) -1-aminoethane;
N, N-bis (pyridin-2-yl-methyl) -1,1-bis (pyridin-2-yl) -2- (pyridin-2-yl) -1-aminoethane;
N, N-bis (pyridin-2-yl-methyl) -1,1-bis (pyridin-2-yl) -2- (pyridin-3-yl) -1-aminoethane;
N, N-bis (pyridin-2-yl-methyl) -1,1-bis (pyridin-2-yl) -2- (pyridin-4-yl) -1-aminoethane;
N, N-bis (pyridin-2-yl-methyl) -1,1-bis (pyridin-2-yl) -2- (1-alkyl-pyridinium-4-yl) -1-aminoethane;
N, N-bis (pyridin-2-yl-methyl) -1,1-bis (pyridin-2-yl) -2- (1-alkyl-pyridinium-3-yl) -1-aminoethane;
N, N-bis (pyridin-2-yl-methyl) -1,1-bis (pyridin-2-yl) -2- (1-alkyl-pyridinium-2-yl) -1-aminoethane.

The most preferred ligands are:
N, N-bis (pyridin-2-ylmethyl) -1,1-bis (pyridin-2-yl) -1-aminoethane, hereinafter referred to as MeN ₄ Py,
N, N-bis (pyridin-2-ylmethyl) -1,1-bis (pyridin-2-yl) -2-phenyl-1-aminoethane, hereinafter referred to as BzN ₄ Py.

Suitable counterions are those which lead to the formation of storage-stable solids. The combination of the preferred iron complexes with the counter ion Y preferably comprises counter-ions selected from RCOO ^-, BPh ₄ ^-, ClO ₄ ^-, BF ₄ ^-, PF ₆ ^-, RSO ₃ ^-, RSO ₄ ^-, SO ₄ ^2-, NO ₃ ^- , F ^- , Cl ^- , Br ^- , I ^{- are} selected, wherein R = H, optionally substituted phenyl, naphthyl or C ₁ -C ₄ alkyl. Preferred coordinating species X are selected from CH ₃ CN, pyridine, H ₂ O, Cl ^- , OR ^- and OOH ^- , wherein R = H, optionally substituted phenyl, naphthyl or C ₁ -C ₄ alkyl.

The effective level of Fe complex catalyst, which is in parts per million (ppm) of iron in an aqueous bleach solution expressed is usually in the range of 0.001 ppm to 100 ppm, preferably between 0.01 ppm and 20 ppm, most preferably between 0.1 ppm and 10 ppm. In industrial bleaching processes, such as textile and pulp bleaching, can higher Levels desired and be used. The lower levels become preferable at laundry washing process used in the household.

The wash bleach composition

The bleaching composition according to the invention has particular application in cleaning formulations to a new and improved wash bleach composition within the scope of the invention comprising a peroxy bleach compound as defined above the aforementioned Fe complex catalyst having the general formula (A), a surface-active Material and a builder include.

Of the Fe complex catalyst is used in the wash bleach composition of Present invention in quantities, so as to the required level in the washing liquid provide. In general, the Fe complex catalyst level corresponds in the wash bleach composition, an iron content of 0.0005 to 0.5% by weight. When the dosage of the wash bleach composition is relative is low, for example about 1-2 g / l, is the Fe content in the formulation corresponding to 0.0025 to 0.5, preferably 0.005 to 0.25 wt .-%. At higher Product dosing, as for example by European consumers used is the Fe content in the formulation is 0.0005 to 0.1, preferably 0.001 to 0.05% by weight.

Laundry bleach compositions of the invention are over a wide pH range between 7 and 13 is effective, with the optimum pH range is between 8 and 11.

The peroxy bleach compound

The Peroxy bleach compound may be a compound that is capable of in a watery solution To give hydrogen peroxide. Hydrogen peroxide sources are in The technique is well known. They include the alkali metal peroxides, organic peroxides, such as urea peroxide, and inorganic persalts, such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulfates. Mixtures of two or more such compounds can be equally suitable.

Especially preferred are sodium perborate tetrahydrate and especially sodium perborate monohydrate. Sodium perborate monohydrate is due to its high content active oxygen is preferred. Sodium percarbonate may be for environmental reasons as well be preferred. The amount thereof in the composition of the invention is for usually in the range from about 5 to 35% by weight, preferably from 10 to 25% by weight, lie.

Another suitable hydrogen peroxide generating system is a combination of a C ₁ -C ₄ alkanol oxidase and a C ₁ -C ₄ alkanol, especially a combination of methanol oxidase (MOX) and ethanol. Such combinations are disclosed in WO-A-9507972, which is incorporated herein by reference.

Alkylhydroxy are another class of peroxy bleach compounds. Examples of this Materials include cumene hydroperoxide and t-butyl hydroperoxide.

auf, worin R eine Alkyl- oder Alkyliden- oder substituierte Alkylengruppe ist, die 1 bis etwa 20 Kohlenstoffatome enthält, gegebenenfalls mit einer inneren Amidbindung; oder eine Phenylen- oder substituierte Phenylengruppe; und Y Wasserstoff, Halogen, Alkyl, Aryl, eine aromatische oder nicht aromatische Imidogruppe, eine -COOH- oder -COOOH-Gruppe oder eine quartäre Ammoniumgruppe ist.Organic peroxyacids may also be suitable as peroxy bleach compounds. Such materials usually have the general formula:

wherein R is an alkyl or alkylidene or substituted alkylene group containing from 1 to about 20 carbon atoms, optionally with an internal amide bond; or a phenylene or substituted phenylene group; and Y is hydrogen, halogen, alkyl, aryl, an aromatic or non-aromatic imido group, a -COOH or -COOOH group or a quaternary ammonium group.

• (i) Peroxybenzoesäure und Ring-substituierte Peroxybenzoesäuren, beispielsweise Peroxy-α-naphthoesäure;
• (ii) aliphatische, substituierte aliphatische und Arylalkylmonoperoxysäuren, beispielsweise Peroxylaurinsäure, Peroxystearinsäure und N,N-Phthaloylaminoperoxycapronsäure (PAP); und
• (iii) 6-Octylamino-6-oxo-peroxyhexansäure.

Typical monoperoxy acids useful herein include, for example:

• (i) peroxybenzoic acid and ring-substituted peroxybenzoic acids, for example, peroxy-α-naphthoic acid;
• (ii) aliphatic, substituted aliphatic and arylalkyl monoperoxyacids, for example peroxylauric acid, peroxystearic acid and N, N-phthaloylaminoperoxycaproic acid (PAP); and
• (iii) 6-octylamino-6-oxo-peroxyhexanoic acid.

• (iv) 1,12-Diperoxydodecandionsäure (DPDA);
• (v) 1,9-diperoxyazelainsäure;
• (vi) Diperoxbrassylsäure; Diperoxysebacinsäure und Diperoxyisphthalsäure;
• (vii) 2-Decyldiperoxybutan-1,4-dionsäure; und
• (viii) 4,4'-Sulfonylbisperoxybenzoesäure.

Typical diperoxyacids useful herein include, for example:

• (iv) 1,12-diperoxydodecanedioic acid (DPDA);
• (v) 1,9-diperoxyazelaic acid;
• (vi) diperoxybrassic acid; Diperoxysebacic acid and diperoxyisphthalic acid;
• (vii) 2-decyldiperoxybutane-1,4-dionic acid; and
• (viii) 4,4'-sulfonylbisperoxybenzoic acid.

As well are inorganic peroxyacid compounds suitable, such as potassium monopersulfate (MPS). Be organic or inorganic peroxyacids As the peroxy compound used, the amount thereof usually becomes in the range of about 2 to 10 wt .-%, preferably from 4 to 8 wt .-%.

All these peroxy compounds can alone or in combination with a peroxyacid bleach precursor and / or an organic Bleach catalyst that is not a transition metal contains be used. In general, the bleaching composition of the Suitably be formulated so that they 2 to 35% by weight, preferably 5 to 25% by weight, of the peroxy bleach contains.

Are peroxyacid bleach precursors are well known and described extensively in the literature, such as in GB-A-836,988, GB-A-864,798, GB-A-907,356, GB-A-1,003,310 and GB-A-1,519,351; DE-A-33,37,921; EP-A-0,185,522, EP-A-0,174,132, EP-A-0,120,591; and US-A-1,246,339, US-A-3,332,882; US Patent 4,128,494, US-A-4,412,934 and US-A-4,675,393.

Another suitable class of peroxyacid bleach precursor is that of the cationic, ie, quaternary ammonium-substituted peroxyacid precursors as disclosed in US-A-4,751,015 and US-A-4,397,757, EP-A-0,284,292 and EP-A-0,331,229. Examples of peroxyacid bleach precursors of this class are:
2- (N, N, N-trimethylammonium) ethyl-sodium-4-sulphophenyl-carbonate-chloride (SPCC),
N-octyl-N, N-dimethyl-N ₁₀ -carbophenoxydecylammonium chloride (ODC);
3- (N, N, N-trimethylammonium) propyl-sodium-4-sulphophenylcarboxylate, and
N, N, N-Trimethylammoniumtoloyloxybenzensulphonat.

A Another special class of bleach precursors is by the cationic Nitriles formed as described in EP-A-303,520; EP-A-458,396 and EP-A-464,880 disclosed.

Everyone This peroxyacid bleach precursor can used in the present invention, although some stronger are preferred as others. From the above classes of bleach precursors the preferred classes are the esters, including acylphenolsulfonates and acylalkylphenolsulfonates; the acylamides; and the quaternary ammonium-substituted ones Peroxysäurepräkursor, including the cationic nitriles.

Examples for the preferred peroxyacid bleach precursor or Activators are sodium 4-benzoyloxy-benzenesulfonate (SBOBS); N, N, N ', N'-tetraacetylethylenediamine (TAED); Sodium 1-methyl-2-benzoyloxybenzen-4-sulfonate; Sodium-4-methyl-3-benzoloxy benzoate; 2- (N, N, N-trimethyl ammonium) ethyl sodium 4-sulfophenyl-carbonatchlorid (SPCC); Trimethylammoniumtoloyloxy-benzenesulfonate; Natriumnonanoyloxybenzensulfonat (SNOBS); Sodium 3,5,5-trimethylhexanoyl oxybenzenesulfonate (STHOBS); and the substituted cationic nitriles.

The precursor can in an amount of up to 12% by weight, more preferably from 2 to 10 Wt .-%, of the composition can be used.

When an alternative to the peroxide generating systems described above For example, molecular oxygen can be used as the oxidant.

The surface active material

The Inventive wash bleach composition contains generally a surface-active material in an amount of 10 to 50% by weight.

The surfactant material may be of natural origin, such as soap, or a synthetic material selected from anionic, nonionic, amphoteric, zwitterionic, cationic actives, and mixtures thereof. Many suitable drugs are commercially available and are described in the literature described in detail, for example in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.

Typical synthetic anionic surfactants are usually water-soluble alkali metal salts of organic sulfates and sulfonates having alkyl groups containing from about 8 to about 22 carbon atoms wherein the term alkyl is intended to include the alkyl portion of higher aryl groups. Examples of suitable synthetic anionic detergent compounds are sodium and ammonium alkyl sulfates, especially those obtained by sulfating higher (C ₈ -C ₁₈ ) alcohols prepared, for example, from tallow or coconut oil, sodium and ammonium alkyl (C ₉ -C ₂₀ ) benzene sulfonates, in particular linear sodium secondary alkyl (C ₁₀ -C ₁₅ ) benzene sulfonates; Sodium alkyl glyceryl ether sulfates, especially the ethers of higher alcohols derived from tallow or coconut oil fatty acid monoglyceride sulfates and sulfonates; Sodium and ammonium salts of sulfuric acid esters of higher (C ₉ -C ₁₈ ) fatty alcohol alkylene oxide, especially ethylene oxide, reaction products; the reaction products of fatty acids, such as coconut fatty acids, which are esterified with isethionic acid and neutralized with sodium hydroxide; Sodium and ammonium salts of fatty acid amides of methyltaurine; Alkane monosulfonates such as those derived from the reaction of alpha-olefins (C ₈ -C ₂₀ ) with sodium bisulfite, and those derived from the reaction of paraffins with SO ₂ and Cl ₂ and then hydrolyzed with a base to give a random To produce sulfonate; Sodium and ammonium (C ₇ -C ₁₂ ) dialkylsulfosuccinates; and olefinsulfonates, the term being used to describe material produced by the reaction of olefins, preferably (C ₁₀ -C ₂₀ ) alpha-olefins, with SO and the subsequent neutralization and hydrolyzation of the reaction product. The preferred anionic detergent compounds are sodium (C ₁₀ -C ₁₅ ) alkyl benzene sulfonates, sodium (C ₁₆ -C ₁₈ ) alkyl ether sulfates.

Examples of suitable nonionic surfactant compounds which can be used, preferably together with the anionic surfactant compounds, include in particular the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C ₆ -C ₂₂ ) phenols, generally from 5 to 25 EO, ie 5 to 25 units of ethylene oxide per molecule; and the condensation products of aliphatic (C ₈ -C ₁₈ ), primary or secondary, linear or branched alcohols with ethylene oxide, generally 2 to 30 EO. Other so-called nonionic surfactants include alkyl polyglycosides, sugar esters, long chain tertiary amine oxides, long chain tertiary phosphine oxides, and dialkyl sulfoxides.

amphoteric or zwitterionic surfactant Connections can also be used in the compositions of the invention, However, this is usually due to their relatively high cost not wished. Will any amphoteric or zwitterionic detergent compounds used, these generally form small amounts in compositions, those on the more widely used synthetic anionic ones and nonionic agents.

As disclosed by EP-A-544,490, the performance of the hereinbefore described bleach catalyst of the active washing system and the detergency builder used in the wash bleach composition of the invention be present, depend.

The wash bleach composition of the invention will preferably comprise from 1 to 15% by weight of an anionic surfactant and from 10 to 40% by weight of a nonionic surfactant. In another preferred embodiment, the active wash system is free of C ₁₆ -C ₁₂ fatty acid soaps.

The builder

The Composition of the invention preferably also contains one Builder in an amount of about 5 to 80 wt .-%, preferably about 10 to 60 wt .-%.

construction materials can from 1) calcium masking materials, 2) precipitating materials, 3) calcium ion exchange materials and 4) mixtures thereof become.

Examples for calcium masking building materials include alkali metal polyphosphates such as sodium tripolyphosphate; nitrilotriacetic and their water-soluble ones salts; the alkali metal salts of carboxymethyloxysuccinic acid, ethylenediaminetetraacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid and Polyacetal carboxylates as described in US-A-4,144,226 and US-A-4,146,495 disclosed.

Examples for precipitate building materials include sodium orthophosphate and sodium carbonate.

Examples for calcium ion exchange building materials include the various types of water-insoluble crystalline or amorphous Aluminosilicates, of which zeolites are the best known representatives, for example Zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070 described.

Especially can the compositions of the invention of any of the organic and inorganic building materials, although for environmental reasons phosphate builders preferably omitted or used only in very small quantities become. Typical builders used in the present invention are usable, for example, sodium carbonate, calcite / carbonate, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyloxymalonate, Carboxymethyloxysuccinat- and the water-insoluble crystalline or amorphous Aluminosilicate building materials, each of which is said to be the major builder either alone or in admixture with smaller amounts of others Builders or polymers are used as co-builders can.

Prefers contains the composition does not exceed 5% by weight of a carbonate builder, expressed as sodium carbonate, stronger preferably not more than 2.5% by weight to almost zero when the pH of the Composition in the lower alkali region is up to 10.

Other ingredients

Regardless of the components already mentioned, the wash bleach composition of the invention may contain any of the conventional adjuvants in amounts in which such materials are normally employed in fabric laundering compositions. Examples of such adjuvants include buffers such as carbonates, foam improvers such as alkanolamides, especially the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, antifoaming agents such as alkyl phosphates and silicones; Antergancing agents such as sodium carboxymethyl cellulose and alkyl or substituted alkyl cellulose ethers; Stabilizers, such as phosphonic acid derivatives (Dequest ^® ie TYPES); softener; inorganic salts and alkaline buffers such as sodium sulfate and sodium silicate; and, usually in very small quantities, fluorescent agents; Fragrances; Enzymes such as proteases, cellulases, lipases, amylases and oxidases; Germicides and colorants.

at the use of a source of hydrogen peroxide, such as sodium perborate or sodium percarbonate, as the bleaching compound contains the composition preferably not more than 5% by weight of a carbonate buffer, expressed as Sodium carbonate, stronger preferably not more than 2.5% by weight to almost zero when the pH of the Composition in the lower alkali region is up to 10.

Of the adjuvants, transition metal sequestrants such as EDTA and phosphonic acid derivatives, for example ethylenediaminetetra (methylenephosphonate) EDTMP-, are of particular interest because they not only enhance the stability of the catalyst / H ₂ O ₂ system and the sensitive ingredients such as enzymes, fluorescers, fragrances and the like, but also improve the bleaching performance, especially in the higher pH range of over 10, especially at pH 10.5 and above.

The Invention will now be apparent from the following non-limiting Examples further illustrated.

example 1

Preparation of the MeN ₄ Py Ligand

The precursor N ₄ Py.HCl ₄ was prepared as follows:

To pyridyl ketone oxime (3 g, 15.1 mmol) was added ethanol (15 ml), concentrated ammonia solution (15 ml) and NH ₄ OAc (1.21 g, 15.8 mmol). The solution was heated to reflux. To this solution was added 4.64 g of Zn in small portions. After the addition of all Zn, the mixture was refluxed for 1 hour and allowed to cool to ambient temperature. The solution was filtered and water (15 ml) was added. Solid NaOH was added until the pH was >> 10, and the solution was extracted with CH ₂ Cl ₂ (3 x 20 mL). The organic layers were dried over Na ₂ SO ₄ and evaporated to dryness. Bis (pyridin-2-yl) methylamine (2.39 g, 12.9 mmol) was obtained as a colorless oil in 86% yield, showing the following analytical features:
¹ H NMR (360 MHz, CDCl _3): δ 2.64 (s, 2H, NH _2), 5.18 (s, 1H, CH), 6.93 (m, 2H, pyridine), 7.22 ( m, 2H, pyridine), 7.41 (m, 2H, pyridine), 8.32 (m, 2H, pyridine);
¹³ C NMR _(CDCl3): δ 62.19 (CH), 121.73 (CH), 122.01 (CH), 136.56 (CH), 149.03 (CH), 162.64 (Cq) ,

To picolyl chloride hydrochloride (4.06 g, 24.8 mmol) at 0 ° C was added 4.9 ml of a 5 N NaOH solution. This emulsion was added by syringe to bis (pyridin-2-yl) methylamine (2.3 g, 12.4 mmol) at 0 ° C. Another 5 ml of a 5 N NaOH solution was added to this mixture. After warming to ambient temperature, the mixture was stirred vigorously for 40 h. The mixture was placed in an ice bath and HClO ₄ was added until pH <1 whereupon a brown solid precipitated. The brown precipitate was collected by filtration and recrystallized from water. While stirring, this mixture was cooled to ambient temperature whereupon a light brown solid precipitated, which was collected by filtration and washed with cold water and air dried (1.47 g).

From 0.5 g of the perchlorate salt of N ₄ Py, prepared as described above, the free amine was obtained by precipitation of the salt with 2 N NaOH and then by extraction with CH ₂ Cl ₂ . To the free amine was added 20 ml of dry tetrahydrofuran, freshly distilled from LiAlH ₄ , under argon. The mixture was stirred and cooled to -70 ° C by an alcohol / dry ice bath. Now, 1 ml of the 2.5 N butyllithium solution in hexane was added, giving an immediately dark red color. The mixture was allowed to warm to -20 ° C and now 0.1 ml of methyl iodide was added. The temperature was kept at -10 ° C for 1 hour. Subsequently, 0.5 g of ammonium chloride was added and the mixture was evaporated in vacuo. To the residue was added water and the aqueous layer was extracted with dichloromethane. The dichloromethane layer was dried over sodium sulfate, filtered and evaporated to give a residue of 0.4 g. The residue was purified by crystallization from ethyl acetate and hexane to give 0.2 g of creamy powder (50% yield), showing the following analytical characteristics:
¹ H NMR (400 MHz, CDCl _3): δ (ppm) 2.05 (s, 3H, CH _3), 4.01 (s, 4H CH _2), 6.92 (m, 2H, pyridine), 7.08 (m, 2H, pyridine), 7.39 (m, 4H, pyridine), 7.60 (m, 2H, pyridine), 7.98 (d, 2H, pyridine), 8.41 (m, 2H, pyridine), 8.57 (m, 2H, pyridine).
¹³ C NMR (100.55 MHz, CDCl _3): δ (ppm) 21.7 _(CH3), 58.2 _(CH2), 73.2 (Cq, 121.4 (CH), 121.7 ( CH), 123.4 (CH), 123.6 (CH), 136.0 (CH), 148.2 (Cq, 148.6 (Cq, 160.1 (Cq, 163.8 (Cq).

Subsequently, [(MeN ₄ Py) Fe (CH ₃ CH)] (ClO ₄ ) ₂ , hereinafter referred to as Fe (MeN ₄ Py), was prepared as follows:

To a solution of 0.27 g of MeN ₄ Py in 12 ml of a mixture of 6 ml of acetonitrile and 6 ml of methanol was added 350 mg of Fe (ClO ₄ ) ₂ .6H ₂ O immediately after a dark red color formed. 0.5 g of sodium perchlorate was then added to the mixture and an orange-red precipitate formed immediately. After 5 minutes of stirring and sonication, the precipitate was isolated by filtration and dried in vacuo at 50 ° C. In this way, 350 mg of orange-red powder was obtained in 70% yield, showing the following analytical features:
¹ H NMR (400 MHz, CD ₃ CN): δ (ppm) 2.15, (CH ₃ CN), 2.28 (s, 3H, CH ₃ ), 4.2 (ab, 4H, CH ₂ ), 7.05 (d, 2H, pyridine), 7.38 (m, 4H, pyridine), 7.71 (2t, 4H, pyridine), 7.98 (t, 2H, pyridine), 8.96 (d, 2H, pyridine), 9.06 (m, 2H, pyridine).
UV / Vis (acetonitrile) [λ max, nm (ε, M ^-1 cm ^-1 )]: 381 (8400), 458 nm (6400).
Anal. Ber. for C ₂₅ H ₂₆ Cl ₂ FeN ₆ O ₈ : C, 46.11; H, 3.87; N, 12,41; Cl, 10.47; Fe, 8.25.
Found: C, 45.49; H, 3.95; N, 12.5; Cl, 10.7; Fe, 8:12.
Bulk ESP (cone voltage 17V in CH ₃ CN): mass / charge 218.6 [MeN ₄ PyFe] ²⁺ ; 239.1 [MeN ₄ PyFeCH ₃ CN] ²⁺ .

Example 2

Preparation of the BzN ₄ Py ligand

To 1 g of the N ₄ Py ligand prepared as described above was added 20 ml of dry tetrahydrofuran, freshly distilled from LiAlH ₄ , under argon. The mixture was stirred and cooled to -70 ° C by an alcohol / dry ice bath. Now, 2 ml of the 2.5N butyllithium solution in hexane was added, giving an immediately dark red color. The mixture was allowed to warm to -20 ° C and now 0.4 ml of benzyl bromide was added. The mixture was allowed to warm up to 25 ° C and stirring was continued overnight. Subsequently, 0.5 g of ammonium chloride was added and the mixture was evaporated in vacuo. To the residue was added water and the aqueous layer was extracted with dichloromethane. The dichloromethane layer was dried over sodium sulfate, filtered and evaporated to give a brown, oily residue of 1 g. According to NMR spectroscopy, the product was not pure but contained no starting material (N ₄ Py). The remainder was used without further purification.

Subsequently, [(BzN ₄ Py) Fe (CH ₃ CN)] (ClO ₄ ) ₂ , hereinafter referred to as Fe (BzN ₄ Py), was prepared as follows:

To a solution of 0.2 g of the residue obtained by the procedure described above in 10 ml of a mixture of 5 ml of acetonitrile and 5 ml of methanol was added 100 mg of Fe (ClO ₄ ) ₂ .6H ₂ O immediately after a dark red color formed. To the mixture was then added 0.25 g of sodium perchlorate and ethyl acetate was allowed to diffuse into the mixture overnight. Some red crystals were formed, which were isolated by filtration and washed with methanol. In this way, 70 mg of a red powder was obtained, showing the following analytical features:
¹ H NMR (400 MHz, CD ₃ CN): δ (ppm) 2.12, (s, 3H, CH ₃ CN), 3.65 + 4.1 (ab, 4H, CH ₂ ), 4.42 ( s, 2H, CH ₂ -benzyl), 6.84 (d, 2H, pyridine), 7.35 (m, 4H, pyridine), 7.45 (m, 3H, benzene), 7.65 (m, 4H Benzene + pyridine), 8.08 (m, 4H, pyridine), 8.95 (m, 4H, pyridine).
UV / Vis (acetonitrile) [λ max, nm (ε, M ^-1 cm ^-1 )]: 380 (7400), 458 nm (5500).
Bulk ESP (cone voltage 17V in CH ₃ CN): mass / charge 256.4 [BzN ₄ Py] ²⁺ ; 612 [BzN ₄ PyFeClO ₄ ] ⁺ .

Example 3

The bleaching activity Fe catalysts, according to the examples 1 and 2 were prepared in the presence of hydrogen peroxide demonstrated on standard tea-stained (BC-1) cotton test garments.

The Experiments were at 40 ° C and at a pH of 10 in a temperature-controlled beaker, that with a magnetic stirrer, a thermocouple and a pH electrode equipped, performed.

Two pieces of the test garment were stirred for 30 minutes in 1 liter of 8.6 x 10 ^-3 mol / l hydrogen peroxide solution in Millipore water containing the concentrations of the compounds as indicated in Table 1. After rinsing with demineralized water, the test clothes were dried in a microwave oven for 7 minutes. The reflectance (R ₄₆₀ *) of the test garments was measured on a Minolta CM 3700d spectrophotometer including ^® UV-filter before and after treatment. The difference (ΔR ₄₆₀ *) between the two reflectivity values thus obtained gives a measurement of bleaching performance, ie, higher ΔR ₄₆₀ * values correspond to improved bleaching performance.

TABLE 1

In Table 1, Fe (MeN ₄ Py) and Fe (BzN ₄ Py) refer to Fe catalysts prepared according to Examples 1 and 2 and Fe (N ₄ Py) to the unmethylated analog as in WO -A-9534628. Blank and Fe (NO ₃ ) ₃ experiments were used as controls.

These measurements show that the significantly improved bleaching performance is obtained with Fe (MeN ₄ Py) and Fe (BzN ₄ Py) as compared to Fe (N ₄ Py) as a catalyst.

Example 4

The bleach activity of the Fe (MeN ₄ Py) catalyst prepared according to Example 1 was demonstrated in the presence of a detergent formulation on standard tea-stained (BC-1) cotton test garments.

The detergent formulation contained the following ingredients and was dosed (in water) as indicated in Table 2. TABLE 2 Detergent formulation used for the bleaching experiments with Fe (MeN ₄ Py) ingredient Dosage (g / l) Linear sodium alkyl benzene sulphonate (LAS) 0.60 Sodium triphosphate (STP) 0.36 sodium 0,44 sodium disilicate 0.20 sodium sulphate 0.67 sodium perborate 0.20 Tetraacetylenedylenediamine (TAED) 0.06 Fe (MeN ₄ Py) <0.01 Enzymes, fluorescent, SCMC, minerals, moisture 0.19

The Experiments were at 25 ° C and at a pH of about 10 (pH of the washing liquid) using of water of 4 ° F (Ca: Mg = 4: 1) in a temperature-controlled beaker, that with a magnetic stirrer, a thermocouple and a pH electrode is performed performed.

• – in Experiment A: 1,5 × 10^–3 Mol/l Wasserstoffperoxid und 0,5 × 10^–3 Mol/l Peroxyessigsäure; und
• – in Experiment B: 2 × 10^–3 Mol/l Wasserstoffperoxid, enthaltend 1 × 10^–5 Mol/l Fe(MeN₄Py).

Two pieces of the test garment were stirred for 30 minutes in 1 liter of the above detergent formulation, yielding in situ:

• In experiment A: 1.5 × 10 ^-3 mol / l hydrogen peroxide and 0.5 × 10 ^-3 mol / l peroxyacetic acid; and
• In experiment B: 2 × 10 ^-3 mol / l hydrogen peroxide containing 1 × 10 ^-5 mol / l Fe (MeN ₄ Py).

After rinsing with demineralized water, the test clothes were dried in a microwave oven for 7 minutes. The reflectance (R ₄₆₀ *) of the ke Testkleidungsstüc was measured on a Minolta CM 3700d spectrophotometer including ^® UV-filter before and after treatment. The difference (ΔR ₄₆₀ *) between the two reflectivity values thus obtained gives a measurement of bleaching performance, ie, higher ΔR ₄₆₀ * values correspond to improved bleaching performance.
Experiment A: 4.0 ΔR ₄₆₀ * bleaching units
Experiment B: 6.7 ΔR ₄₆₀ * bleaching units

These measurements show that the significantly improved bleaching performance with Fe (MeN ₄ Py) / H ₂ O _{2 is obtained} in the corresponding detergent formulation as compared to peroxyacetic acid / H ₂ O ₂ in the same detergent formulation.

Example 5

The Dye oxidation activity Fe catalysts, according to the examples 1 and 2 were prepared in the presence of hydrogen peroxide demonstrated on a dye known as Acid Red 88.

The experiments were performed at 40 ° C at pH = 10 in a 1 cm cuvette in the presence of 8.6 x 10 ^-3 mol / l hydrogen peroxide and 6 x 10 ^-5 mol / l Acid Red 88. The absorbance at 503 nm (A ₅₀₃ ), which is the maximum of the characteristic visible absorbance of the dyes in aqueous media, was measured at t = 0 and t = 30 minutes. The ΔA ₅₀₃ value given in the table is a measurement of dye bleach activity: ΔA ₅₀₃ = 1 - (A ₅₀₃ (t = 30) / A ₅₀₃ (t = 0 min)), expressed in%.

A higher ΔA ₅₀₃ represents better dye bleach activity.

TABLE 3

Fe (MeNaPy) and Fe (BzN ₄ Py) in Table 2 refer to the Fe catalyst prepared according to Examples 1 and 2. Blank and Fe (NO ₃ ) ₃ experiments were used as controls.

The measurements show that the improved dye oxidation performance is obtained when Fe (MeN ₄ Py) and Fe (BzN ₄ Py) are used as catalysts, especially at pH 8.

Example 6

The oxidation activity of the Fe (MeN ₄ Py) catalyst prepared according to Example 1 was demonstrated in the presence of hydrogen peroxide over a range of organic substrates. The experiments were carried out at ambient temperature in acetone. The concentration of the Fe catalyst was 7.7 × 10 ^-4 M, and the catalyst / H ₂ O ₂ / substrate ratio was 1/100/1000. The turnover numbers given in Table 4 represent the number of molecules formed per molecule of catalyst as determined by the indicated reaction time using gas chromatography. In a blank experiment or in the presence of Fe (NO ₃ ) ₃ , essentially no oxidation products could be detected.

TABLE 4

Claims (9)

Bleaching and oxidation catalyst comprising an Fe complex having the formula (A): LFeX _n ] ^z Y _q (A) or precursors thereof, wherein Fe is iron in the oxidation number II, III, IV or V; X represents a coordinating species such as H ₂ O, ROH, NR _3, RCN, OH ^-, OOH ^-, RS ^-, RO ^-, RCOO ^-, OCN ^-, SCN ^-, N ₃ ^-, CN ^-, F ^-, Cl ^-, Br ^-, I ^-, O ^2-, NO ₃ ^-, NO ₂ ^-, SO ₄ ^2-, SO ₃ ^2-, PO ₄ ^3- or aromatic N donors such as pyridines, pyrazines, pyrazoles, Imidazle, benzimidazoles , Pyrimidines, triazoles and thiazoles, wherein R is H, optionally substituted alkyl or optionally substituted aryl; n is an integer between 0 and 3; Y is a counterion, the type of which depends on the charge of the complex; z indicates the charge of the complex and is an integer that may be positive, zero or negative; when Y z is positive, is an anion such as F ^-, Cl ^-, Br ^-, I ^-, NO ₃ ^-, BPh ₄ ^-, ClO ₄ ^-, BF ₄ ^-, PF ₆ ^-, RSO ₃ ^-, RSO ₄ ^-, SO _{4 is} ^2- , CF ₃ SO ₃ ^- or RCOO ^- ; when z is negative, Y is a common cation such as an alkali metal, alkaline earth metal or (alkyl) ammonium cation; q = z / [charge Y]; L represents a ligand of the general formula (B):

wherein R ₂ , R ₃ , R ₄ , R _{5 are} independently selected from C ₀ -C ₅ alkyl substituted with a pyridine ring, and R _{1 is} C ₀ -C ₂₀ alkylaryl, C ₀ -C ₂₀ alkyl heteroaryl or C0-C ₂₀ alkyl and is other than H. Catalyst according to claim 1, wherein X represents a coordinating species selected from CH ₃ CN, pyridine, H ₂ O, Cl ^- , OOH ^- and OR ^- , wherein R is hydrogen, optionally substituted phenyl, naphthyl or C ₁ -C ₄ alkyl is. Catalyst according to claim 1 or 2, wherein the counterion Y from RCOO ^- , BPh ₄ ^- , F ^- , Cl ^- , Br ^- , I ^- , ClO ₄ ^- , BF ₄ ^- , PF ₆ ^- , RSO ₃ ^- , RSO ₄ ^{2 -} SO ₄ ^2- and NO ₃ ^{- is} selected, wherein R = H, optionally substituted phenyl, naphthyl or C ₁ -C ₄ alkyl. A catalyst according to any one of claims 1 to 3, wherein the ligand L N, N-bis (pyridin-2-ylmethyl) -1,1-bis (pyridin-2-yl) -1-aminoethane is. A catalyst according to any one of claims 1 to 3, wherein the ligand L N, N-bis (pyridin-2-ylmethyl) -1,1-bis (pyridin-2-yl) -2-phenyl-1-aminoethane is. A bleaching composition comprising a peroxy bleach compound and a catalyst according to any one of the preceding claims. A composition according to claim 6 which is the peroxy bleach compound at a level of from 2 to 35% by weight and the catalyst at one Level corresponding to an iron content of 0.0005 to 0.5% by weight. A composition according to claim 6 or 7, wherein the Peroxy bleach compound of hydrogen peroxide, hydrogen peroxide-releasing or -producing compounds, peroxyacids and their salts and mixtures thereof optionally together with peroxyacid bleach precursor. A composition according to any one of claims 6 to 8, the moreover a surface active Material in an amount of 10 to 50 wt .-% and a builder in an amount of 5 to 80% by weight.