EP0783035A2 - Bleaching system containing Bis-and-Tris-(mu-oxo)-di-manganese complex salts - Google Patents

Bleaching system containing Bis-and-Tris-(mu-oxo)-di-manganese complex salts Download PDF

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EP0783035A2
EP0783035A2 EP96120743A EP96120743A EP0783035A2 EP 0783035 A2 EP0783035 A2 EP 0783035A2 EP 96120743 A EP96120743 A EP 96120743A EP 96120743 A EP96120743 A EP 96120743A EP 0783035 A2 EP0783035 A2 EP 0783035A2
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formula
alkyl
bleaching agent
bis
agent systems
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EP96120743A
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German (de)
French (fr)
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EP0783035B1 (en
EP0783035A3 (en
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Ahmed Dr. Tafesh
Matthias Prof. Dr. Beller
Vera Friderichs
Gerd Dr. Reinhardt
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Clariant Produkte Deutschland GmbH
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes

Definitions

  • Bleaches that release active oxygen are an essential part of modern washing and cleaning agents. Its main task is to remove stubborn stains such as tea, coffee, red wine or fruit juices from textile fibers or solid surfaces. This is done by oxidative destruction of the chromophoric system; At the same time, adhering microorganisms are killed and odorants neutralized.
  • Hydrogen peroxide, organic or inorganic peracid are mostly used as bleaching agents.
  • a persalt is usually used as a source of active oxygen in powdery products.
  • Typical examples are sodium perborates or percarbonates or urea adducts.
  • bleach activators are often added.
  • Examples include tetraacetylethylenediamine (TAED), diacetyldioxohexahydrotriazine (DADHT), pentaacetylglycose (PAG), benzoyloxibenzenesulfonate (BOBS) and nonanoyloxibenzenesulfonate (NOBS).
  • TAED tetraacetylethylenediamine
  • DADHT diacetyldioxohexahydrotriazine
  • PAG pentaacetylglycose
  • BOBS benzoyloxibenzenesulfonate
  • NOBS nonanoyloxibenzenesulfonate
  • transition metals in free or complex form catalyze the decomposition of hydrogen peroxides.
  • the effectiveness of the compounds described so far is unsatisfactory in most cases.
  • the addition of metal salts leads to catalytic decomposition of the hydrogen peroxide, but no bleaching effect is observed. This is usually associated with damage to the textile fabric. The occurrence of free transition metals during the washing and cleaning process is therefore undesirable.
  • the metal salt is used in complexed form, the corresponding complex must be stable to hydrolysis and oxidation during storage and under conditions of use in order to suppress these side effects.
  • EP A 458 397 and 458 398 describes the use of macrocyclic polyamines as complex ligands in multinuclear, oxygen-bridged manganese complexes. In combination with oxidizing agents, especially on tea stains, these complexes show good bleaching properties.
  • the difficult to access complex ligand of the triazacyclononane type has a disadvantage. It is only accessible in a multi-stage, by-product-rich manufacturing process. Similar complexes are described in EP 544 519, again the synthesis of the complex ligand is very complex and difficult to implement on an industrial scale.
  • L is preferably a ligand of the formula II.
  • R is preferably C 1 -C 4 -alkyl, in particular methyl.
  • anion A are Cl - , Br - , J - , NO 3 - , ClO 4 - , NCS - , PF 6 - , RSO 3 - , RSO 4 - , SO 4 2- , BPh 4 - , OAc - .
  • Preferred anions are PF 6 - , ClO 4 - , tosylate.
  • the ligands of the formula III contained in these manganese complex salts are prepared by reacting 2- (chloromethyl) pyridinium chloride with an alkylenediamine in the presence of a phase transfer catalyst (see Synthesis, June 1992, p. 539-540) or in an analogous manner for the substituted other ligands of formula III.
  • the ligands of the formula II are prepared in the same way by reacting 2- (chloromethyl) pyridinium chloride or analogous pyridinium compounds with an amine R-NH 2 .
  • the manganese complex salts of the formula I are prepared in accordance with the information in Inorg. Chem.
  • the metal complexes can either be added to the washing and cleaning agent in prefabricated form or generated in situ from the ligand and transition metal during the washing process.
  • the bleaching catalysts are used in combination with an oxidizing agent.
  • oxidizing agents that can be used are hydrogen peroxide, alkali metal perborates, percarbonates, perphosphates or persulfates. If the catalysts are used in powdery products, sodium perborate mono- or tetrahydrate, caroate in the form of the triple salt and sodium percarbonate, the latter in particular in coated form, are particularly preferred. These compounds can be used either with the catalysts alone or, in accordance with a preferred embodiment, additionally together with a bleach activator. This extends the range of applications and strengthens the germicidal properties of the formulation.
  • Bleach activators are known from numerous patent applications. Examples of these are reactive esters and amides such as in GB 836,988, 864,798, 907,356, 1,003,310 and 1,519,351; EP 284,292, 331,229, 303,520, 185,522, 174,132, 120,591 and US 1,246,339, 3,332,882, 4,128,494, 4,412,934, 4,675,393, 4,751,015 and 4,397,757.
  • organic peroxycarboxylic acids can also be used directly as oxidizing agents.
  • Typical representatives are peroxibenzoic acid and substituted derivatives, aliphatic mono- and dicarboxylic acids such as pernonanoic acid, perlauric acid, 1,9-diperoxiazeldic acid and 1,12-dodecanediperic acid.
  • N, N'-phthaloylaminoperoxycarboxylic acids such as N, N'-phthaloylaminoperoxihexanoic acid (PAP), 6-octylamino-6-oxoperoxihexanoic acid, monoperoxiphthalic acid and its salts, 2-alkylperoxi-1,4-butanedioic acids or 4,4'-sulphonylbisperoxiboesoes.
  • composition of the bleaching agent system according to the invention can vary within wide limits and is generally between 0.0005 to 2% by weight, preferably 0.001 to 0.5% by weight of the bleaching catalyst described and 1 to 99.9995%, preferably 5 to 99.999 % of an oxidizing agent from the group of inorganic or organic peracids or persalt, and optionally 0 to 70%, preferably 10 to 60% of a bleach activator.
  • the bleaching systems according to the invention are used in heavy-duty detergents, multi-component detergents (modular systems), stain salts, stain pretreatment agents, machine dishwashing detergents, cleaning agents for hard surfaces, disinfectants and denture cleaners.
  • the catalysts also act as dye transfer inhibitors.
  • the catalysts are normally added to the washing and cleaning agent in granular form.
  • Inorganic salts such as sodium sulfate, chloride, phosphate or silicates can be used as granulation aids. In a preferred application form, they are incorporated into the activator granulate.
  • inorganic or organic auxiliaries can be used for granulation, film-forming materials such as surfactants, fatty acids, celulose derivatives or polymers are preferred.
  • the granules can additionally be provided with a coating, which on the one hand increases their storage stability and interactions with other detergent ingredients can be prevented during storage, but on the other hand their release kinetics can also be influenced.
  • the bleach system according to the invention can be added to the washing and cleaning agents in the form of a powder or as granules.
  • washing and cleaning agents normally also contain surface-active compounds such as anionic, nonionic, zwitterionic, amphoteric or cationic surfactants, builders, enzymes and additives.
  • Surfactants can be of natural or synthetic origin and are e.g. in "Surface Active Agents and Detergents" Volumes I and II by Schwartz, Perry and Berch. Examples are alkyl sulfates, alkyl sulfonates, alkylarylsulfonates, alpha-sulfofatty acid methyl esters, soaps and alkyl ether sulfonates. Nonionic surfactants such as alkyl polyglycol ethers, alkyl polyglucosides, glucamides, sugar esters and amine oxides can also be used.
  • Important builder and cobuilder substances which can be used in combination with the bleaching system according to the invention are phosphates such as sodium tripolyphosphate, zeolites of the types A, X and P, alkali metal carbonates and bicarbonates, amorphous and crystalline silicates, in particular layered silicates such as SKS-6, 7, 9 or 10 from Hoechst AG or disilicates such as those sold by Akzo under the trade name Britesil ® .
  • Organic carboxylic acids such as citric acid or amino acids can be used as co-builders, but also polymers of the polyacrylic acid type or copolymers of acrylic acid and maleic acid or their derivatives. Phosphonate or other complexing agents can also be added.
  • Amylase, proteases, lipases, cellulases and peroxidases can be used as enzymes, cellulose ethers, silicones, bentonites, optical brighteners and perfume as further additives.
  • N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,2-ethylenediamine were dissolved in 30 ml of a mixture of ethanol and water (5: 1) and then Mn (acetate) 3 ⁇ 2H 2 O (0.96 g; 3.6 mmol) was added. Then was 2.2 g (20 mmol) sodium butyrate were added and then 2 ml HClO 4 (70%). A pH of 7.5 was established. Then 3 g (24.48 mmol) NaClO 4 were added and this mixture was stirred for 4 hours at room temperature.
  • TAED tetraacetylethylene diamine
  • Example 3 Washing tests in a Linitest device
  • Example 3 The tests were carried out as described in Example 3. Instead of the test soil tea (BC-1), beetroot and curry on cotton (manufacturer laundry research Krefeld) were used. catalyst Beetroot ⁇ RE Curry ⁇ RE without 0 0 K1 + 2.0 + 0.6 K4 + 1.1 + 0.1 K2 + 4.0 + 0.9
  • the bleaching results on the test soils beetroot and curry can also be significantly increased.
  • the washing tests were carried out in the Linitest réelle at 40 ° C; Washing time 30 min. 1.5 g / l WMP were pre-dissolved in 200 ml water (15 ° dH) and 0.5 g / l sodium perborate monohydrate was added. Before the start of the washing tests, 0; 1.5; 3; 6; 12; 25 mg / l of the catalysts added. The washing tests were carried out analogously to Example 3. The table shows the reflectance differences ⁇ RE of the washes with and without a catalyst.
  • Example 7 Influence of various oxidizing agents on the bleaching result

Abstract

Bleach systems contain bis- and tris-( mu -oxo)-di-manganese complex salts of formula (I) ÄLMn( mu -O)a( mu -OAc)bMnLÜ (x+) Ay; in which Ac = 2-8C acyl; a = 1-3; b = 0 if a = 2 or 3 or b = 2 if a = 1; x = 2 or 3; A = a mono- or di-valent anion; y = the equivalent amount of anion A to balance the positive charges; L = a ligand of formula R-N(Q)2 (II) or (Q)2N-(C(R<1>)2)g-N(Q)2 (III); Q = a group of formula (i); R = 1-12C alkyl, 5-10C cycloalkyl, phenyl, NH2, NHR<2>, N(R<2>)2, OH, OR<2> or COOH; R<1> = H, 1-12C alkyl, 5-10C cycloalkyl, NH2, NHR<2>, N(R<2>)2, OH, OR<2>, COOH, COOR<2>, Cl, Br, F or CN; R<2> = 1-12C alkyl or 5-10C cycloalkyl; g = 2 or 3; m, n = 0-4. Also claimed are washing agents and cleaning agents containing this bleach system.

Description

Bleichmittel, die aktiven Sauerstoff freisetzen, sind ein wesentlicher Bestandteil moderner Wasch- und Reinigungsmittel. Ihre Hauptaufgabe ist die Entfernung hartnäckiger Anschmutzungen wie Tee, Kaffee, Rotwein oder Fruchtsäften von textilen Fasern oder festen Oberflächen. Dies erfolgt durch oxidative Zerstörung des chromophoren Systems; gleichzeitig werden anhaftende Mikroorganismen abgetötet und Geruchsstoffe neutralisiert.Bleaches that release active oxygen are an essential part of modern washing and cleaning agents. Its main task is to remove stubborn stains such as tea, coffee, red wine or fruit juices from textile fibers or solid surfaces. This is done by oxidative destruction of the chromophoric system; At the same time, adhering microorganisms are killed and odorants neutralized.

Als bleichendes Agens werden meist Wasserstoffperoxid, organische oder anorganische Persäure verwendet. In pulverförmigen Produkten wird als Quelle für aktiven Sauerstoff meist ein Persalz eingesetzt. Typische Beispiele dafür sind Natriumperborate oder -percarbonate oder Harnstoffaddukte.Hydrogen peroxide, organic or inorganic peracid are mostly used as bleaching agents. A persalt is usually used as a source of active oxygen in powdery products. Typical examples are sodium perborates or percarbonates or urea adducts.

Um die Wirksamkeit dieser Perverbindungen im Temperaturbereich von 40 bis 60°C zu steigern, werden vielfach Bleichaktivatoren zugesetzt. Beispiele hierfür sind Tetraacetylethylendiamin (TAED), Diacetyldioxohexahydrotriazin (DADHT), Pentaacetylglycose (PAG), Benzoyloxibenzolsulfonat (BOBS) und Nonanoyloxibenzolsulfonat (NOBS). In Gegenwart des Aktivators werden aus den Persalzen die entsprechenden Persäuren freigesetzt, die meist ein breiteres Wirkspektrum aufweisen als Wasserstoffperoxid.In order to increase the effectiveness of these per compounds in the temperature range from 40 to 60 ° C., bleach activators are often added. Examples include tetraacetylethylenediamine (TAED), diacetyldioxohexahydrotriazine (DADHT), pentaacetylglycose (PAG), benzoyloxibenzenesulfonate (BOBS) and nonanoyloxibenzenesulfonate (NOBS). In the presence of the activator, the corresponding peracids are released from the persalts, which usually have a broader activity spectrum than hydrogen peroxide.

In vielen Fällen führt aber auch die Kombination eines Persalzes mit einem Aktivator noch nicht zu den optimalen Bleicheigenschaften. Problematisch ist insbesondere die eingeschränkte Wirksamkeit solcher Bleichsysteme bei niederen Anwendungstemperaturen und ihre fehlende Reaktivität gegenüber bestimmten Anschmutzungen.In many cases, however, the combination of a persalt with an activator does not yet lead to the optimal bleaching properties. A particular problem is the limited effectiveness of such bleaching systems at low application temperatures and their lack of reactivity to certain types of soiling.

Wünschenswert sind daher Systeme mit weiter gesteigerter Leistung. Aus ökonomischen und ökologischen Gründen werden katalytisch wirkende Additive bevorzugt. Daneben besteht aber auch ein Bedarf an Katalysatoren, die direkt mit Wasserstoffperoxid oder Caroaten reagieren und durch die die Aktivatorkonzentration deutlich reduziert oder überflüssig wird.Systems with further increased performance are therefore desirable. For economic and ecological reasons, catalytically active additives are preferred. However, there is also a need for catalysts which react directly with hydrogen peroxide or caroates and which significantly reduce or eliminate the activator concentration.

Es ist seit vielen Jahren bekannt, daß Übergangsmetalle in freier oder komplexierter Form die Zersetzung von Wasserstoffperoxiden katalysieren. Die Wirksamkeit der bisher beschriebenen Verbindungen ist aber in den meisten Fällen unbefriedigend. Vielfach führt der Zusatz von Metallsalzen zwar zu einer katalytischen Zersetzung des Wasserstoffperoxids, ein Bleicheffekt wird jedoch nicht beobachtet. Meist ist dies mit einer Schädigung des textilen Gewebes verbunden. Das Auftreten freier Übergangsmetalle während des Wasch- und Reinigungsprozesses ist daher unerwünscht. Wird dagegen das Metallsalz in komplexierter Form verwendet muß der entsprechende Komplex während der Lagerung und unter Anwendungsbedingungen hydrolyse- und oxidationsstabil sein, um diese Nebenwirkungen zu unterdrücken.It has been known for many years that transition metals in free or complex form catalyze the decomposition of hydrogen peroxides. The effectiveness of the compounds described so far is unsatisfactory in most cases. In many cases, the addition of metal salts leads to catalytic decomposition of the hydrogen peroxide, but no bleaching effect is observed. This is usually associated with damage to the textile fabric. The occurrence of free transition metals during the washing and cleaning process is therefore undesirable. If, on the other hand, the metal salt is used in complexed form, the corresponding complex must be stable to hydrolysis and oxidation during storage and under conditions of use in order to suppress these side effects.

Komplexe des Kupfers oder Cobalts mit Pyridincarbonsäure oder -dicarbonsäure sind in US 3,156,654 beschrieben. US 3,532,634 lehrt die Verwendung von Picolinsäuren, Pyrrolidincarbonsäuren oder Phenanthrolin. In US 4,430,243 werden EDTA und EDTMP-Komplexe von Kupfer, Eisen und Mangan als Bleichkatalysatoren beansprucht, nach US 4,478,733 können Mangansalze in Waschmittelformulierungen auf Basis Zeolith/Ortophosphat erfolgreich verwendet werden. Als effektive Komplexierungsmittel für Übergangsmetalle wurden zudem Hydroxicarbonsäuren (EP A 237 111), Porphinsysteme (EP A 306 089), 2,2'-Bispyridylamine (EP A 392 592), Salen-Derivate (EP A 408 131), makrocyclische Polyamine (EP A 439 387) oder Polyole wie Sorbitol (EP A 443 651) beschrieben. Aus ökologischen Gründen wird meist Mangan als Zentralatom gewählt, daneben sind aber auch Komplexe von Eisen, Kupfer und Cobalt bekannt.Complexes of copper or cobalt with pyridine carboxylic acid or dicarboxylic acid are described in US 3,156,654. US 3,532,634 teaches the use of picolinic acids, pyrrolidine carboxylic acids or phenanthroline. US 4,430,243 claims EDTA and EDTMP complexes of copper, iron and manganese as bleaching catalysts; US 4,478,733 successfully uses manganese salts in detergent formulations based on zeolite / ortophosphate. Hydroxyarboxylic acids (EP A 237 111), porphine systems (EP A 306 089), 2,2'-bispyridylamines (EP A 392 592), salen derivatives (EP A 408 131), macrocyclic polyamines (EP A 439 387) or polyols such as sorbitol (EP A 443 651). For ecological reasons, manganese is mostly chosen as the central atom, but complexes of iron, copper and cobalt are also known.

EP A 458 397 und 458 398 beschreibt die Verwendung von macrocyclischen Polyaminen als Komplexliganden in mehrkernigen, sauerstoffverbrückten Mangankomplexen. Diese Komplexe zeigen in Kombination mit Oxidationsmitteln, insbesondere an Tee-Anschmutzungen, gute Bleicheigenschaften. Als nachteilig wirkt sich allerdings der schwer zugängliche Komplexligand vom Triazacyclononan-Typ aus. Er ist nur in einem mehrstufigen, nebenproduktreichen Herstellprozeß zugänglich. In EP 544 519 sind ähnliche Komplexe beschrieben, wiederum ist die Synthese des Komplexliganden sehr aufwendig und großtechnisch schwer zu realisieren.EP A 458 397 and 458 398 describes the use of macrocyclic polyamines as complex ligands in multinuclear, oxygen-bridged manganese complexes. In combination with oxidizing agents, especially on tea stains, these complexes show good bleaching properties. However, the difficult to access complex ligand of the triazacyclononane type has a disadvantage. It is only accessible in a multi-stage, by-product-rich manufacturing process. Similar complexes are described in EP 544 519, again the synthesis of the complex ligand is very complex and difficult to implement on an industrial scale.

Es besteht daher auch weiterhin ein Bedarf an einfach herzustellenden, effektiven Bleichkatalysatoren mit breiten Wirkspektren zum Einsatz in Wasch- und Reinigungsmitteln.There is therefore still a need for easy-to-produce, effective bleaching catalysts with a broad spectrum of activity for use in detergents and cleaning agents.

Überraschenderwise wurde nun gefunden, daß sich die im folgenden beschriebenen Mangankomplexsalze ausgezeichnet zum Einsatz in Wasch- und Reinigungsmitteln eignen und bereits in katalytischen Mengen die Wirksamkeit von Wasserstoffperoxid, Peressigsäure und anderen Bleichsystemen um ein Mehrfaches steigern. Von besonderem Vorteil gegenüber dem Stand der Technik erweist sich die leichte Zugänglichkeit dieser Katalysatoren.Surprisingly, it has now been found that the manganese complex salts described below are excellently suitable for use in detergents and cleaning agents and increase the effectiveness of hydrogen peroxide, peracetic acid and other bleaching systems by a multiple even in catalytic amounts. The easy accessibility of these catalysts has proven to be particularly advantageous over the prior art.

Gegenstand der Erfindung sind Bleichmittelsysteme enthaltend Bis- und Tris-(µ-oxo)-di-Mangan-Komplexsalze der Formel I

        [LMn(µ-O)a(µ-OAc)bMnL]xAy     (I)

worin

Ac
eine C2-C8-Acylgruppe ist,
a
ist 1, 2 oder 3,
b
ist 0, wenn a 2 oder 3 ist oder b ist 2, wenn a 1 ist,
x
bezeichnet die Anzahl der positiven Ladungen und ist 2 oder 3,
A
ist ein ein- oder zweifach negativ geladenes Anion,
y
bedeutet die für den Ausgleich der positiven Ladungen erforderliche equivalente Menge an Anion A und
L
bedeutet einen Liganden der Formel II oder III
Figure imgb0001
 worin R C1-C12-Alkyl, C5-C10-Cycloalkyl, Phenyl, NH2, NHR2, N(R2)2, OH, OR2 oder COOH, R1 Wasserstoff, C1-C12-Alkyl, C5-C10-Cycloalkyl, NH2, NHR2, N(R2)2, OH, OR2, COOH, COOR2, Cl, Br, F oder CN, R2 C1-C12-Alkyl oder C5-C10-Cycloalkyl bedeuten, g 2 oder 3 und m und n Null oder eine ganze Zahl von 1 bis 4 ist.The invention relates to bleaching agent systems containing bis- and tris (μ-oxo) -di-manganese complex salts of the formula I.

[LMn (µ-O) a (µ-OAc) b MnL] x A y (I)

wherein
Ac
is a C 2 -C 8 acyl group,
a
is 1, 2 or 3,
b
is 0 if a is 2 or 3 or b is 2 if a is 1,
x
denotes the number of positive charges and is 2 or 3,
A
is a single or double negatively charged anion,
y
means the equivalent amount of anion A and required to balance the positive charges
L
means a ligand of formula II or III
Figure imgb0001
 wherein RC 1 -C 12 alkyl, C 5 -C 10 cycloalkyl, phenyl, NH 2 , NHR 2 , N (R 2 ) 2 , OH, OR 2 or COOH, R 1 is hydrogen, C 1 -C 12 alkyl , C 5 -C 10 cycloalkyl, NH 2 , NHR 2 , N (R 2 ) 2 , OH, OR 2 , COOH, COOR 2 , Cl, Br, F or CN, R 2 C 1 -C 12 alkyl or C 5 -C 10 cycloalkyl, g is 2 or 3 and m and n is zero or an integer from 1 to 4.

Bevorzugt sind Liganden der Formeln II und III, bei denen alle Substituenten R1 in den Liganden L Wasserstoff bedeuten und n = 1 ist. Für den Fall a = 3 und b = 0, ist L vorzugsweise ein Ligand der Formel II. Bevorzugt sind auch Komplexsalze der Formel I, worin a = 1 und b = 2 ist und L einen Liganden der Formel II bedeutet. Bei Verbindungen der Formel I, worin L einen Liganden der Formel II bedeutet, ist R vorzugsweise C1-C4-Alkyl, insbesondere Methyl. Als Anion A kommen in Frage Cl-, Br-, J-, NO3 -, ClO4 -, NCS-, PF6 -, RSO3 -, RSO4 -, SO4 2-, BPh4 -, OAc-. Bevorzugte Anionen sind PF6 -, ClO4 -, Tosylat.Ligands of the formulas II and III are preferred in which all the substituents R 1 in the ligands L are hydrogen and n = 1. For the case a = 3 and b = 0, L is preferably a ligand of the formula II. Also preferred are complex salts of the formula I, in which a = 1 and b = 2 and L is a ligand of the formula II. In the case of compounds of the formula I in which L is a ligand of the formula II, R is preferably C 1 -C 4 -alkyl, in particular methyl. As anion A are Cl - , Br - , J - , NO 3 - , ClO 4 - , NCS - , PF 6 - , RSO 3 - , RSO 4 - , SO 4 2- , BPh 4 - , OAc - . Preferred anions are PF 6 - , ClO 4 - , tosylate.

Die Herstellung der in diesen Mangan-Komplexsalzen enthaltenen Liganden der Formel III erfolgt durch Umsetzung von 2-(Chlormethyl)pyridiniumchlorid mit einem Alkylendiamin in Gegenwart eines Phasentransferkatalysators (s. Synthesis, June 1992, p. 539-540) bzw. in analoger Weise für die substituierten anderen Liganden der Formel III. In gleicher Weise werden die Liganden der Formel II hergestellt durch Umsetzung von 2-(Chlormethyl)-pyridiniumchlorid bzw. von analogen Pyridiniumverbindungen mit einem Amin R-NH2. Die Herstellung der Mangan-Komplexsalze der Formel I erfolgt entsprechend den Angaben in Inorg. Chem. 1989, 28, 3606-3608, indem man eine wäßrige Lösung, die MnCl2 und den Liganden enthält, mit H2O2 oxidiert oder analog zu dem in Inorg. Chem. 1994, 33, 4105-4111 beschriebenen Verfahren, bei dem die Oxidation mit Ammoniumperoxodisulfat vorgenommen wird.The ligands of the formula III contained in these manganese complex salts are prepared by reacting 2- (chloromethyl) pyridinium chloride with an alkylenediamine in the presence of a phase transfer catalyst (see Synthesis, June 1992, p. 539-540) or in an analogous manner for the substituted other ligands of formula III. The ligands of the formula II are prepared in the same way by reacting 2- (chloromethyl) pyridinium chloride or analogous pyridinium compounds with an amine R-NH 2 . The manganese complex salts of the formula I are prepared in accordance with the information in Inorg. Chem. 1989, 28, 3606-3608 by oxidizing an aqueous solution containing MnCl 2 and the ligand with H 2 O 2 or analogously to that in Inorg. Chem. 1994, 33, 4105-4111 described method, in which the oxidation is carried out with ammonium peroxodisulfate.

Beispiele für besonders bevorzugte Komplexliganden sind:

  • N,N'-bis(2-pyridylmethyl)-N-methylamin
  • N,N,N',N'-Tetrakis(2-pyridylmethyl)-1,2-ethylendiamin
  • N,N,N',N'-Tetrakis(2-pyridylmethyl)-1,3-propylendiamin
  • N,N,N',N'-Tetrakis(2-pyridylethyl)-1,3-propylendiamin
  • N,N,N',N'-Tetrakis(2-pyridylethyl)-1,4-butylendiamin
Examples of particularly preferred complex ligands are:
  • N, N'-bis (2-pyridylmethyl) -N-methylamine
  • N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,2-ethylenediamine
  • N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,3-propylenediamine
  • N, N, N ', N'-tetrakis (2-pyridylethyl) -1,3-propylenediamine
  • N, N, N ', N'-tetrakis (2-pyridylethyl) -1,4-butylenediamine

Die Metallkomplexe können entweder in vorgefertigter Form dem Wasch- und Reinigungsmittel zugegeben oder während des Waschprozesses aus Ligand und Übergangsmetall insitu generiert werden.The metal complexes can either be added to the washing and cleaning agent in prefabricated form or generated in situ from the ligand and transition metal during the washing process.

Beispiele für erfindungsgemäß zu verwendende Komplexsalze sind:

  • Bis(µ-oxo)bis[N,N,N',N'-tetrakis(2-pyridylmethyl)-1,2-ethylendiamin]-dimangan(III,IV)Perchlorat
  • Tris(µ-oxo)bis[N,N,N',N'-tetrakis(2-pyridylmethyl)-1,2-ethylendiamin]-dimangan(IV,IV)Hexafluorophosphat
  • (µ-Oxo)bis(µ-OAc)bis[N,N,N',N'-tetrakis(2-pyridylmethyl)-1,2-ethylendiamin]-dimangan(III,III)Perchlorat
  • (µ-Oxo)bis(µ-OBu)bis[N,N,N',N'-tetrakis(2-pyridylmethyl)-1,2-ethylendiamin]-dimangan(III,III)Perchlorat
  • Tris(µ-oxo)bis[N,N,N',N'-tetrakis(2-pyridylmethyl)-1,3-propylendiamin]-dimangan(IV,IV)Hexafluorophosphat
  • Bis(µ-oxo)bis[N,N'-bis(2-pyridylmethyl)-N-methylamin]-dimangan(III,IV)Perchlorat
  • Tris(µ-oxo)bis[N,N'-bis(2-pyridylmethyl)-N-methylamin]-dimangan(IV,IV)Hexafluorophosphat
  • (µ-Oxo)bis(µ-OBu)bis[N,N'-bis(2-pyridylmethyl)-N-methylamin]-dimangan(IV,IV)Hexafluorophosphat
Examples of complex salts to be used according to the invention are:
  • Bis (µ-oxo) bis [N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,2-ethylenediamine] -dimangan (III, IV) perchlorate
  • Tris (µ-oxo) to [N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,2-ethylenediamine] dimangane (IV, IV) hexafluorophosphate
  • (µ-Oxo) to (µ-OAc) to [N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,2-ethylenediamine] -dimangane (III, III) perchlorate
  • (µ-Oxo) to (µ-OBu) to [N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,2-ethylenediamine] -dimangane (III, III) perchlorate
  • Tris (µ-oxo) to [N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,3-propylenediamine] dimangane (IV, IV) hexafluorophosphate
  • Bis (µ-oxo) bis [N, N'-bis (2-pyridylmethyl) -N-methylamine] -dimangan (III, IV) perchlorate
  • Tris (µ-oxo) bis [N, N'-bis (2-pyridylmethyl) -N-methylamine] dimangane (IV, IV) hexafluorophosphate
  • (µ-Oxo) to (µ-OBu) to [N, N'-bis (2-pyridylmethyl) -N-methylamine] dimangane (IV, IV) hexafluorophosphate

Diese Komplexsalze besitzen katalytische Eigenschaften und sind in der Lage die Bleichleistung von Persäuren, Persalzen oder Wasserstoffperoxid im Wasch- und Reinigungsprozeß beträchtlich zu steigern.These complex salts have catalytic properties and are able to considerably increase the bleaching performance of peracids, persalts or hydrogen peroxide in the washing and cleaning process.

In den erfindungsgemäßen Bleichmittelsystemen werden die Bleichkatalysatoren in Kombination mit einem Oxidationsmittel eingesetzt. Beispiele solcher Oxidationsmittel, die Verwendung finden können, sind Wasserstoffperoxid, Alkalimetallperborate, -percarbonate, -perphosphate oder -persulfate. Besonders bevorzugt werden, wenn die Katalysatoren in pulverförmigen Produkten eingesetzt werden, Natriumperborat Mono- oder Tetrahydrat, Caroat in Form des Tripelsalzes und Natriumpercarbonat, letzteres insbesondere in gecoateter Form. Diese Verbindungen können entweder mit den Katalysatoren allein oder gemäß einer bevorzugten Ausführungsform, zusätzlich zusammen mit einem Bleichaktivator verwendet werden. Hierdurch wird das Anwendungsspektrum erweitert und die keimabtötenden Eigenschaften der Formulierung verstärkt.In the bleaching agent systems according to the invention, the bleaching catalysts are used in combination with an oxidizing agent. Examples of such oxidizing agents that can be used are hydrogen peroxide, alkali metal perborates, percarbonates, perphosphates or persulfates. If the catalysts are used in powdery products, sodium perborate mono- or tetrahydrate, caroate in the form of the triple salt and sodium percarbonate, the latter in particular in coated form, are particularly preferred. These compounds can be used either with the catalysts alone or, in accordance with a preferred embodiment, additionally together with a bleach activator. This extends the range of applications and strengthens the germicidal properties of the formulation.

Bleichaktivatoren sind aus zahlreichen Patentanmeldungen bekannt. Beispiele hierfür sind reaktive Ester und Amide wie in GB 836,988, 864,798, 907,356, 1,003,310 und 1,519,351; EP 284,292, 331,229, 303,520, 185,522, 174,132, 120,591 und US 1,246,339, 3,332,882, 4,128,494, 4,412,934, 4,675,393, 4,751,015 und 4,397,757 beschrieben. Besonders bevorzugt sind Tetraacetylethylendiamin, Nonanoyloxibenzolsulfonat, Benzoyloxibenzolsulfonat, Nonanoyl- und Benzoylcaprolactam, Isatosäure-, Malen-, Bernstein- und Zitronensäureanhydride sowie acylierte Zucker oder Zuckerderivate, daneben Alkyl- oder Arylnitrile.Bleach activators are known from numerous patent applications. Examples of these are reactive esters and amides such as in GB 836,988, 864,798, 907,356, 1,003,310 and 1,519,351; EP 284,292, 331,229, 303,520, 185,522, 174,132, 120,591 and US 1,246,339, 3,332,882, 4,128,494, 4,412,934, 4,675,393, 4,751,015 and 4,397,757. Tetraacetylethylenediamine, nonanoyloxibenzenesulfonate, benzoyloxibenzenesulfonate, nonanoyl and benzoylcaprolactam, isatoic acid, maleic, succinic and citric acid anhydrides and acylated sugar or sugar derivatives, in addition alkyl or aryl nitriles, are particularly preferred.

An Stelle des Aktivatorsystems (Persalz plus Bleichaktivator) können auch bestimmte organische Peroxicarbonsäuren als Oxidationsmittel direkt Verwendung finden. Typische Vertreter sind Peroxibenzoesäure und substituierte Derivate, aliphatische Mono- und Dicarbonsäuren wie Pernonansäure, Perlaurinsäure, 1,9-Diperoxiazeldinsäure und 1,12-Dodecandipersäure. Weitere Beispiele sind N,N'-Phthaloylaminoperoxicarbonsäuren wie N,N'-Phthaloylaminoperoxihexansäure (PAP), 6-Octylamino-6-oxoperoxihexansäure, Monoperoxiphthalsäure und ihre Salze, 2-Alkylperoxi-1,4-butandisäuren oder 4,4'-Sulphonylbisperoxibenzoesäure.Instead of the activator system (persalt plus bleach activator), certain organic peroxycarboxylic acids can also be used directly as oxidizing agents. Typical representatives are peroxibenzoic acid and substituted derivatives, aliphatic mono- and dicarboxylic acids such as pernonanoic acid, perlauric acid, 1,9-diperoxiazeldic acid and 1,12-dodecanediperic acid. Further examples are N, N'-phthaloylaminoperoxycarboxylic acids such as N, N'-phthaloylaminoperoxihexanoic acid (PAP), 6-octylamino-6-oxoperoxihexanoic acid, monoperoxiphthalic acid and its salts, 2-alkylperoxi-1,4-butanedioic acids or 4,4'-sulphonylbisperoxiboesoes.

Die Zusammensetzung des erfindungsgemäßen Bleichmittelsystems kann in weiten Grenzen schwanken und liegt im allgemeinen zwischen 0,0005 bis 2 Gew.-%, vorzugsweise 0,001 bis 0,5 Gew.-% des beschriebenen Bleichkatalysators und 1 bis 99,9995 %, vorzugsweise 5 bis 99,999 % eines Oxidationsmittels aus der Gruppe der anorganischen oder organischen Persäuren oder Persalze, und gegebenenfalls 0 bis 70 %, vorzugsweise 10 bis 60 % eines Bleichmittelaktivators.The composition of the bleaching agent system according to the invention can vary within wide limits and is generally between 0.0005 to 2% by weight, preferably 0.001 to 0.5% by weight of the bleaching catalyst described and 1 to 99.9995%, preferably 5 to 99.999 % of an oxidizing agent from the group of inorganic or organic peracids or persalt, and optionally 0 to 70%, preferably 10 to 60% of a bleach activator.

Die erfindungsgemäßen Bleichsysteme finden Verwendung in Vollwaschmitteln, Mehrkomponentenwaschmitteln (Baukastensysteme), Fleckensalzen, Fleckenvorbehandlungsmitteln, Maschinengeschirrspülmitteln, Reinigungsmitteln für harte Oberflächen, Desinfektionsmitteln, und Gebißreinigern. Neben der Bleiche übernehmen die Katalysatoren auch die Funktion von Dye-Transfer-Inhibitoren. Normalerweise werden die Katalysatoren in granulierter Form dem Wasch- und Reinigungsmittel zugesetzt. Als Granulierhilfsmittel können dabei anorganische Salze wie Natriumsulfat, -chlorid, -phosphat oder Silikate verwendet werden. In einer bevorzugten Anwendungsform werden sie in das Aktivatorgranulat eingearbeitet. Zur Granulierung können dem Stand der Technik entsprechend anorganische oder organische Hilfsstoffe verwendet werden, bevorzugt sind filmbildende Materialien wie Tenside, Fettsäuren, Celulosederivate, oder Polymere. Die Granulate können zusätzlich mit einem Coating versehen sein, wodurch zum einen ihre Lagerstabilität erhöht und Wechselwirkungen mit anderen Waschmittelinhaltsstoffen während der Lagerung unterbunden werden können, zum anderen aber auch ihre Auslösekinetik beeinflußt werden kann.The bleaching systems according to the invention are used in heavy-duty detergents, multi-component detergents (modular systems), stain salts, stain pretreatment agents, machine dishwashing detergents, cleaning agents for hard surfaces, disinfectants and denture cleaners. In addition to bleaching, the catalysts also act as dye transfer inhibitors. The catalysts are normally added to the washing and cleaning agent in granular form. Inorganic salts such as sodium sulfate, chloride, phosphate or silicates can be used as granulation aids. In a preferred application form, they are incorporated into the activator granulate. According to the state of the art, inorganic or organic auxiliaries can be used for granulation, film-forming materials such as surfactants, fatty acids, celulose derivatives or polymers are preferred. The granules can additionally be provided with a coating, which on the one hand increases their storage stability and interactions with other detergent ingredients can be prevented during storage, but on the other hand their release kinetics can also be influenced.

Üblicherweise werden die erfindungsgemäßen Bleichmittelsysteme, bestehend aus Katalysator und Oxidationsmittel und gegebenenfalls Aktivator, in den Wasch- und Reinigungsmitteln in folgenden Konzentrationen eingesetzt:

  • Vollwaschmittel: 2 bis 40 Gew.-%
  • Fleckensalze und Wäschevorbehandlungsmittel: 20 bis 100 Gew.-%
  • Maschinengeschirrspülmittel: 1 bis 30 Gew.-%
  • Reinigungsmittel für harte Oberflächen und Desinfektionsreiniger: 2 bis 50 Gew.-%
  • Gebißreiniger: 2 bis 20 Gew.-%
The bleaching agent systems according to the invention, consisting of catalyst and oxidizing agent and optionally activator, are usually used in the washing and cleaning agents in the following concentrations:
  • Heavy duty detergent: 2 to 40% by weight
  • Stain salts and laundry pretreatment agents: 20 to 100% by weight
  • Dishwasher detergent: 1 to 30% by weight
  • Hard surface cleaner and disinfectant cleaner: 2 to 50% by weight
  • Denture cleaner: 2 to 20% by weight

Das erfindungsgemäße Bleichmittelsystem kann den Wasch- und Reinigungsmitteln in Form eines Pulvers oder als Granulat zugesetzt werden.The bleach system according to the invention can be added to the washing and cleaning agents in the form of a powder or as granules.

Neben dem Bleichmittelsystem enthalten die Wasch- und Reinigungsmittel normalerweise noch oberflächenaktive Verbindungen wie anionischen, nichtionische, zwitterionische, amphoterische oder kationische Tenside, Builder, Enzyme und Additive.In addition to the bleach system, the washing and cleaning agents normally also contain surface-active compounds such as anionic, nonionic, zwitterionic, amphoteric or cationic surfactants, builders, enzymes and additives.

Tenside können natürlichen oder synthetischen Ursprungs sein und sind z.B. in "Surface Active Agents and Detergents" Band I und II von Schwartz, Perry und Berch beschrieben. Beispiele sind Alkylsulfate, Alkylsulfonate, Alkylarylsulfonate, alpha-Sulfofettsäuremethylester, Seifen und Alkylethersulfonate. Nichtionische Tenside wie Alkylpolyglykolether, Alkylpolyglucoside, Glucamide, Zuckerester und Aminoxide können ebenfalls verwendet werden.Surfactants can be of natural or synthetic origin and are e.g. in "Surface Active Agents and Detergents" Volumes I and II by Schwartz, Perry and Berch. Examples are alkyl sulfates, alkyl sulfonates, alkylarylsulfonates, alpha-sulfofatty acid methyl esters, soaps and alkyl ether sulfonates. Nonionic surfactants such as alkyl polyglycol ethers, alkyl polyglucosides, glucamides, sugar esters and amine oxides can also be used.

Wichtige Builder- und Cobuildersubstanzen, die in Kombination mit den erfindungsgemäßen Bleichmittelsystemen verwendet werden können, sind Phosphate wie Natriumtripolyphosphat, Zeolithe vom Typ A, X und P, Alkalimetallcarbonate und -hydrogencarbonate, amorphe und kristalline Silikate, insbesondere Schichtsilikate wie SKS-6, 7, 9 oder 10 der Hoechst AG oder Disilikate wie sie von Akzo unter dem Handelsnamen Britesil® vertrieben werden. Als Co-Builder können u.a. organische Carbonsäuren wie Zitronensäure oder Aminosäuren verwendet werden, daneben aber auch Polymere vom Typ der Polyacrylsäure oder Mischpolymerisate aus Acrylsäure und Maleinsäure oder deren Derivate. Weiterhin können Phosphonat oder andere Komplexbildner zugesetzt werden.Important builder and cobuilder substances which can be used in combination with the bleaching system according to the invention are phosphates such as sodium tripolyphosphate, zeolites of the types A, X and P, alkali metal carbonates and bicarbonates, amorphous and crystalline silicates, in particular layered silicates such as SKS-6, 7, 9 or 10 from Hoechst AG or disilicates such as those sold by Akzo under the trade name Britesil ® . Organic carboxylic acids such as citric acid or amino acids can be used as co-builders, but also polymers of the polyacrylic acid type or copolymers of acrylic acid and maleic acid or their derivatives. Phosphonate or other complexing agents can also be added.

Als Enzyme können Amylase, Proteasen, Lipasen, Cellulasen und Peroxidasen, als weitere Additive Celluloseether, Silikone, Bentonite, optische Aufheller und Parfum verwendet werden.Amylase, proteases, lipases, cellulases and peroxidases can be used as enzymes, cellulose ethers, silicones, bentonites, optical brighteners and perfume as further additives.

Beispiele für die Herstellung der Katalysatoren.Examples of the preparation of the catalysts. Beispiel 1example 1 (µ-Oxo)bis(µ-acetato)bis[N,N,N',N'-tetrakis(2-pyridylmethyl-)1,2-ethylendiamin]-di-mangan IV,IV-perchlorat (Katalysator K1)(µ-oxo) to (µ-acetato) to [N, N, N ', N'-tetrakis (2-pyridylmethyl-) 1,2-ethylenediamine] -di-manganese IV, IV-perchlorate (catalyst K1)

Eine Mischung aus 25,5 ml Ethanol und 4,5 ml Wasser wurde durch dreimaliges Anlegen eines Vakuums entgast und mit Argon behandelt, um alle Reste an Sauerstoff zu entfernen, die sonst eine Oxidation von MnII zu MnIV bewirken würden. Zu dieser Mischung wurden 2,47 g (5,82 mmol) N,N,N',N'-Tetrakis(2-pyridylmethyl)-ethylendiamin gegeben. Man erhielt eine gelbe Lösung mit einem pH-Wert von 8,8. Dann wurden 0,96 g (3,6 mmol) Mangantriacetat (Mn(OAc)3·2H2O) zugegeben. Die Lösung wurde braun und wies einen pH-Wert von 6,2 auf. Anschließend wurden 2 g (14,58 mmol) Natriumacetat zugegeben (pH 6,5), dann Perchlorsäure (55 Tropfen) bis zu einem pH-Wert von 5. Nach Zugabe von 3 g (24,48 mmol) Natriumperchlorat fiel bei pH 6,1 ein Niederschlag aus. Die Reaktionsmischung wurde 4 Stunden lang gerührt. Die ausgefallenen Kristalle wurden abgefiltert und unter Stickstoff getrocknet. Man erhielt 3,08 g Rohprodukt der Verbindung (µ-Oxo) bis (µ-acetato)bis[N,N,N',N'-tetrakis-(2-pyridylmethyl-)1,2-ethylendiamin-]di-mangan-IV,IV-perchlorat. Analyse: ber.: Mn 8,39 % C 51,35 % H 4,92 % N 12,83 % O 17,1 % gef.: Mn 8,4 % C 48,0 % H 4,9 % N 12,7 % O 17,9 % A mixture of 25.5 ml of ethanol and 4.5 ml of water was degassed by applying a vacuum three times and treated with argon to remove any residual oxygen which would otherwise cause oxidation of MnII to MnIV. 2.47 g (5.82 mmol) of N, N, N ', N'-tetrakis (2-pyridylmethyl) ethylenediamine were added to this mixture. A yellow solution with a pH of 8.8 was obtained. Then 0.96 g (3.6 mmol) of manganese triacetate (Mn (OAc) 3 · 2H 2 O) was added. The solution turned brown and had a pH of 6.2. 2 g (14.58 mmol) of sodium acetate were then added (pH 6.5), then perchloric acid (55 drops) to a pH of 5. After addition of 3 g (24.48 mmol) of sodium perchlorate, the pH dropped to 6 , 1 a precipitation. The reaction mixture was stirred for 4 hours. The precipitated crystals were filtered off and dried under nitrogen. 3.08 g of crude product of the compound (μ-oxo) bis (μ-acetato) to [N, N, N ', N'-tetrakis (2-pyridylmethyl-) 1,2-ethylenediamine-] di-manganese were obtained -IV, IV perchlorate. Analysis: calc .: Mn 8.39% C 51.35% H 4.92% N 12.83% O 17.1% found: Mn 8.4% C 48.0% H 4.9% N 12.7% O 17.9%

Beispiel 2Example 2 (µ-Oxo)bis(µ-butyrato)bis[N,N,N',N'-tetrakis(2-pyridylmethyl-)1,2-ethylen-di-amin]dimangan III,IV perchlorat (Katalysator K2)(µ-oxo) to (µ-butyrato) to [N, N, N ', N'-tetrakis (2-pyridylmethyl-) 1,2-ethylene-di-amine] dimangan III, IV perchlorate (catalyst K2)

2,47 (5,82 mmol) N,N,N',N'-Tetrakis-(2-pyridylmethyl)-1,2-ethylendiamin wurden in 30 ml einer Mischung aus Ethanol und Wasser (5:1) gelöst und anschließend Mn(Acetat)3·2H2O (0,96 g; 3,6 mmol) hinzugegeben. Dann wurde 2,2 g (20 mmol) Natriumbutyrat zugegeben und anschließend 2 ml HClO4 (70 %ig). Es stellte sich ein pH-Wert von 7,5 ein. Dann wurden 3 g (24,48 mmol) NaClO4 zugegeben und diese Mischung wurde 4 Stunden bei Raumtemperatur gerührt. Es bildete sich ein Niederschlag, der abfiltriert, mit einer Ethanol/Wasser-Mischung (85 % EtOH/15 % H2O) gewaschen und getrocknet wurde. Rohausbeute 2,3 g. Der Feststoff wurde mit 70 ml Aceton behandelt und die Aceton-Lösung von den unlöslichen anorganischen Salzen abfiltriert. Nach Abdestillation des Acetons und Umkristallisation mit Ethanol/Wasser 5:1 erhielt man das oben genannte Komplexsalz. Analyse: ber.: Mn 7,5 % C 49,17 % H 4,95 % N 11,47 % gef.: Mn 8,0% C 44,8 % H 4,5 % N 12,1 % 2.47 (5.82 mmol) N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,2-ethylenediamine were dissolved in 30 ml of a mixture of ethanol and water (5: 1) and then Mn (acetate) 3 · 2H 2 O (0.96 g; 3.6 mmol) was added. Then was 2.2 g (20 mmol) sodium butyrate were added and then 2 ml HClO 4 (70%). A pH of 7.5 was established. Then 3 g (24.48 mmol) NaClO 4 were added and this mixture was stirred for 4 hours at room temperature. A precipitate formed which was filtered off, washed with an ethanol / water mixture (85% EtOH / 15% H 2 O) and dried. Crude yield 2.3 g. The solid was treated with 70 ml of acetone and the acetone solution was filtered off from the insoluble inorganic salts. After distilling off the acetone and recrystallization with ethanol / water 5: 1, the above-mentioned complex salt was obtained. Analysis: calc .: Mn 7.5% C 49.17% H 4.95% N 11.47% found: Mn 8.0% C 44.8% H 4.5% N 12.1%

Beispiel 3Example 3 Tris(µ-oxo)bis[N,N,N',N'-tetrakis(2-pyridylmethyl-]1,3-diaminopropan-di-mangan-IV,IV-Hexafluorphosphat (Katalysator K3)Tris (µ-oxo) to [N, N, N ', N'-tetrakis (2-pyridylmethyl-] 1,3-diaminopropane-di-manganese-IV, IV-hexafluorophosphate (catalyst K3)

3,5 g (19 mmol) KPF6 und 3,86 g (8,8 mmol) N,N,N',N'-tetrakis-(2-pyridylmethyl-)1,3-diaminopropan wurden bei 5°C zu 120 ml einer Äthanol/-Wasser-Mischung (5:1) zugegeben und gerührt. Die Lösung verfärbte sich gelb und es wurden 3,48 g (17,6 mmol) MnCl2·4H2O zugegeben. Zu der schwach gelben Lösung wurden dann 20 ml H2O2 (3 %ig) und 5,2 ml NaOH (20 %ig) zugegeben. Die Temperatur stieg auf 12°C und das Reaktionsgemisch verfärbte sich braun. Die Reaktionsmischung wurde dann 1 Stunde lang auf 5°C gekühlt und dann 2 Stunden bei Raumtemperatur gehalten. Die Lösemittel wurden im Vakuum abdestilliert und das angefallene Rohprodukt wurde mit Aceton behandelt um überschüssiges Mangandioxid zu entfernen. Analyse: ber.: C 35,86 % H 3,75 % N 9,29 % gef.: C 33,8 % H 3,2 % N 8,3 % 3.5 g (19 mmol) of KPF 6 and 3.86 g (8.8 mmol) of N, N, N ', N'-tetrakis (2-pyridylmethyl-) 1,3-diaminopropane were added at 5 ° C 120 ml of an ethanol / water mixture (5: 1) added and stirred. The solution turned yellow and 3.48 g (17.6 mmol) of MnCl 2 .4H 2 O were added. 20 ml of H 2 O 2 (3%) and 5.2 ml of NaOH (20%) were then added to the pale yellow solution. The temperature rose to 12 ° C and the reaction mixture turned brown. The reaction mixture was then cooled to 5 ° C for 1 hour and then kept at room temperature for 2 hours. The solvents were distilled off in vacuo and the resulting crude product was treated with acetone to remove excess manganese dioxide. Analysis: calc .: C 35.86% H 3.75% N 9.29% found: C 33.8% H 3.2% N 8.3%

Beispiel 4Example 4 Tris-(µ-oxo)bis[N,N'-bis(2-pyridylmethyl-)N-methylamin]dimangan IV,IV hexafluorophosphat (Katalysator K4)Tris (µ-oxo) bis [N, N'-bis (2-pyridylmethyl-) N-methylamine] dimangane IV, IV hexafluorophosphate (catalyst K4)

1,74 g (8,8 mmol) MnCl2·4H2O, 1,88 g (8,8 mmol) N,N'-bis-(2-pyridylmethyl)-N-methylamin und 1,75 g (9,5 mmol) KPF6 wurden in 600 ml einer Mischung aus Ethanol und Wasser (2:1) gelöst. Die Lösung wurde 20 Min. bei Raumtemperatur gerührt und dann im Eisbad auf 5°C gekühlt. Dann wurden 10 ml H2O2 (3 %ig) und 2,6 ml einer 20 %igen wäßrigen NaOH-Lösung zugegeben, wobei die Temperatur auf 10°C anstieg und ein Niederschlag ausfiel. Diese Mischung wurde 1 Stunde lang bei 5°C und eine weitere Stunde bei 20°C gerührt. Der Niederschlag wurde abfiltriert und mit Wasser gewaschen. Rohausbeute 6,1 g. Nach dem Trocknen wurde der Feststoff mit Aceton behandelt, wobei MnO2 als Feststoff zurückblieb. Die Acetonlösung wurde vom unlöslichen MnO2 abfiltriert und das Aceton abdestilliert. Man erhielt 1,25 g eines grau-grünen Feststoffs. Analyse: ber.: C 40,9 % H 3,8 % N 10,9 % gef.: C 35,0 % H 3,6 % N  9,42 % 1.74 g (8.8 mmol) of MnCl 2 · 4H 2 O, 1.88 g (8.8 mmol) of N, N'-bis- (2-pyridylmethyl) -N-methylamine and 1.75 g (9 , 5 mmol) KPF 6 were dissolved in 600 ml of a mixture of ethanol and water (2: 1). The solution was stirred for 20 minutes at room temperature and then cooled to 5 ° C. in an ice bath. Then 10 ml H 2 O 2 (3%) and 2.6 ml of a 20% aqueous NaOH solution were added, the temperature rising to 10 ° C. and a precipitate falling out. This mixture was stirred at 5 ° C for 1 hour and at 20 ° C for an additional hour. The precipitate was filtered off and washed with water. Crude yield 6.1 g. After drying, the solid was treated with acetone, leaving MnO 2 as a solid. The insoluble MnO 2 was filtered off from the acetone solution and the acetone was distilled off. 1.25 g of a gray-green solid were obtained. Analysis: calc .: C 40.9% H 3.8% N 10.9% found: C 35.0% H 3.6% N 9.42%

Beispiel 5Example 5 (µ-Oxo)bis(µ-butyrato)bis[N,N'-bis(2-pyridylmethyl-)N-methylamin]-di-mangan-IV,IV-perchlorat (Katalysator K5)(µ-oxo) to (µ-butyrato) to [N, N'-bis (2-pyridylmethyl-) N-methylamine] -di-manganese-IV, IV-perchlorate (catalyst K5)

Eine Mischung von 25,5 ml Ethanol und 4,5 ml Wasser wurde durch dreimaliges Anlegen eines Vakuums und Einleiten von Argon frei von Sauerstoff gemacht. Zu dieser Mischung wurden 1,25 g (5,82 mmol) N,N'-bis(2-pyridylmethyl)-N-methylamin in Form einr Lösung in 25,5 ml Ethanol und 4,5 ml Wasser zugegeben. Der Reaktionsansatz verfärbte sich braun. Dann wurden 0,96 g (3,6 mmol) Mn(Acetat)3·2H2O zugegeben und nachdem sich der Reaktionsansatz dunkelbraun verfärbt hatte, wurden 2,2 g (20 mmol) Natriumbutyrat zugegeben. Dann wurden 1,8 ml HClO4 (70 %ig) zugegeben, wobei der pH-Wert von 5,0 erreicht wurde, und anschließend 3,0 g (24,48 mmol) NaClO4. Nach 4 Stunden wurde der erhaltene Niederschlag abfiltriert, um überschüssiges Mangandioxid zu entfernen. Das Lösemittel wurde aus dem Filtrat abdestilliert und nach Umkristallisation mit 20 ml Isopropanol erhielt man die Titelverbindung als weißen Feststoff.A mixture of 25.5 ml of ethanol and 4.5 ml of water was made free of oxygen by applying a vacuum three times and introducing argon. 1.25 g (5.82 mmol) of N, N'-bis (2-pyridylmethyl) -N-methylamine in the form of a solution in 25.5 ml of ethanol and 4.5 ml of water were added to this mixture. The reaction mixture turned brown. Then 0.96 g (3.6 mmol) of Mn (acetate) 3 .2H 2 O was added and after the reaction mixture had turned dark brown, 2.2 g (20 mmol) Sodium butyrate added. Then 1.8 ml of HClO 4 (70%) were added, the pH having reached 5.0, and then 3.0 g (24.48 mmol) of NaClO 4 . After 4 hours the precipitate obtained was filtered off to remove excess manganese dioxide. The solvent was distilled off from the filtrate and after recrystallization with 20 ml of isopropanol, the title compound was obtained as a white solid.

Als Vergleichsverbindungen wurden Mangan(II)sulfat und der 4-zähnige Mangankomplex Bis(µ-oxo)bis[N,N'-bis(2-pyridylmethyl)-N,N'-dimethyl-1,2-ethylendiamin]-dimangan(III,IV) Perchlorat (Katalysator V1) verwendet.Manganese (II) sulfate and the 4-toothed manganese complex bis (µ-oxo) bis [N, N'-bis (2-pyridylmethyl) -N, N'-dimethyl-1,2-ethylenediamine] -dimangan ( III, IV) perchlorate (catalyst V1) used.

Anwendungstechnische BeispieleApplication engineering examples Beispiel 1: Stabilität von Wasserstoffperoxid in Gegenwart der KatalysatorenExample 1: Stability of hydrogen peroxide in the presence of the catalysts

0,5 g Natriumperborat-Monohydrat wurden in 1 l Wasser (15°dH) gelöst und auf 20°C temperiert. Nach Zugabe von 4 mg einer Manganverbindung wurde die Wasserstoffperoxidkonzentration in Abhängigkeit von der Zeit durch jodometrische Titration verfolgt.0.5 g of sodium perborate monohydrate was dissolved in 1 l of water (15 ° dH) and heated to 20 ° C. After adding 4 mg of a manganese compound, the hydrogen peroxide concentration was monitored as a function of time by iodometric titration.

Gehalt an Wasserstoffperoxid in der LösungHydrogen peroxide content in the solution

Figure imgb0002
Figure imgb0002

Die Ergebnisse zeigen, daß die erfindungsgemäßen Katalysatoren im Gegensatz zu freien Manganionen Wasserstoffperoxid nicht unkontrolliert zersetzen.The results show that, in contrast to free manganese ions, the catalysts according to the invention do not decompose hydrogen peroxide in an uncontrolled manner.

Beispiel 2: Stabilität von Peressigsäure in Gegenwart der KatalysatorenExample 2: Stability of peracetic acid in the presence of the catalysts

1 g Natriumpercarbonat und 0,5 g TAED-Pulver (TAED: Tetraacetylethylendiamin) werden zusammen mit 0,01 g der Manganverbindung in 1 l Wasser (15°dH) gegeben, das auf 40°C temperiert ist. Die freigesetzte Menge an Peressigsäure wird in Abhängigkeit von der Zeit durch jodometrische Titration bestimmt.1 g of sodium percarbonate and 0.5 g of TAED powder (TAED: tetraacetylethylene diamine) are added together with 0.01 g of the manganese compound in 1 l of water (15 ° dH), which is heated to 40 ° C. The amount of peracetic acid released is determined as a function of time by iodometric titration.

Gehalt an Peressigsäure in der LösungPeracetic acid content in the solution

Figure imgb0003
Figure imgb0003

Die Ergebnisse zeigen, daß weder die Freisetzung der Persäure noch ihre Stabilität in wäßriger Lösung durch die erfindungsgemäßen Katalysatoren wesentlich beeinflußt werden. Eine unkontrollierte Zersetzung durch Metallspuren findet nicht statt.The results show that neither the release of the peracid nor its stability in aqueous solution are significantly influenced by the catalysts according to the invention. An uncontrolled decomposition by metal traces does not take place.

Beispiel 3: Waschversuche im LinitestgerätExample 3: Washing tests in a Linitest device

2 g/l Testwaschmittel (P-frei, WMP, Wäschereiforschung Krefeld) wurden in 200 ml Wasser (15°dH) gelöst. Anschließend wurden 1 g/L Natriumpercarbonat und 0,5 g/L TAED und jeweils 4 Lappen einer Testanschmutzung (Tee auf Baumwolle, BC-1, Wäschereiforschung Krefeld) hinzugegeben. Die Waschversuche wurden bei 40°C in einem Linitest-Gerät der Fa. Haraeus, Hanau, durchgeführt, Waschdauer 30 min. Der Weißgrad der Wäsche wurde anschließend mit einem Elrepho-Gerät (Fa. Datacolor) bestimmt. In einer zweiten Versuchsreihe wurden die Versuche unter Zugabe von 10 mg/L eines Katalysators durchgeführt. In den Ergebnistabelle sind die Remissionsdifferenzen (Wäsche mit Katalysator) - (Wäsche ohne Katalysator) aufgeführt. Katalysator ΔRE ohne 0 K1 + 5,9 K2 + 6,5 K3 + 5,5 K4 + 5,8 K5 + 5,2 Mn2SO4 + 4,3 V1 + 5,0 2 g / l test detergent (P-free, WMP, laundry research Krefeld) was dissolved in 200 ml water (15 ° dH). Then 1 g / L sodium percarbonate and 0.5 g / L TAED and 4 rags each of a test soil (tea on cotton, BC-1, laundry research Krefeld) were added. The Washing tests were carried out at 40 ° C. in a Linitest device from Haraeus, Hanau, washing time 30 minutes. The whiteness of the laundry was then determined using an Elrepho device (from Datacolor). In a second series of experiments, the experiments were carried out with the addition of 10 mg / L of a catalyst. The remission differences (washing with catalyst) - (washing without catalyst) are listed in the results table. catalyst ΔRE without 0 K1 + 5.9 K2 + 6.5 K3 + 5.5 K4 + 5.8 K5 + 5.2 Mn 2 SO 4 + 4.3 V1 + 5.0

Die Ergebnisse zeigen die Überlegenheit der erfindungsgemäßen Katalysatoren auf Basis 3- und 6-zähniger Komplexliganden gegenüber freien Manganionen und dem nicht erfindungsgemäßen Katalysator V1.The results show the superiority of the catalysts according to the invention based on 3- and 6-dentate complex ligands over free manganese ions and the catalyst V1 not according to the invention.

Beispiel 4: Waschversuche im LinitestgerätExample 4: Washing tests in the Linitest device

Die Versuche wurden wie in Beispiel 3 beschrieben durchgeführt. Anstelle der Testanschmutzung Tee (BC-1) wurden Rote Bete und Curry auf Baumwolle (Hersteller Wäschereiforschung Krefeld) verwendet. Katalysator Rote Bete ΔRE Curry ΔRE ohne 0 0 K1 + 2,0 + 0,6 K4 + 1,1 + 0,1 K2 + 4,0 + 0,9 The tests were carried out as described in Example 3. Instead of the test soil tea (BC-1), beetroot and curry on cotton (manufacturer laundry research Krefeld) were used. catalyst Beetroot ΔRE Curry ΔRE without 0 0 K1 + 2.0 + 0.6 K4 + 1.1 + 0.1 K2 + 4.0 + 0.9

Durch den Einsatz der erfindungsgemäßen Katalysatoren lassen sich auch die Bleichergebnisse an den Testanschmutzungen Rote Bete und Curry deutlich steigern.By using the catalysts according to the invention, the bleaching results on the test soils beetroot and curry can also be significantly increased.

Beispiel 5: Konzentrationsabhängigkeit der katalysierten Wasserstoffperoxid-BleicheExample 5: Concentration dependence of the catalyzed hydrogen peroxide bleach

Die Waschversuche wurden im Linitestgerät bei 40°C durchgeführt; Waschzeit 30 min. 1,5 g/l WMP wurden in 200 ml Wasser (15°dH) vorgelöst und 0,5 g/l Natriumperborat-Monohydrat hinzugegeben. Vor Beginn der Waschversuche wurden 0; 1,5; 3; 6; 12; 25 mg/l der Katalysatoren hinzugefügt. Die Waschversuche wurden analog Beispiel 3 durchgeführt. In der Tabelle aufgeführt sind die Remissionsdifferenzen ΔRE der Wäschen mit und ohne Katalysator. Katalysator Katalysator-Konzentration [mg/l] 0 1,5 3 6 12 25 K1 0 + 2,0 + 2,0 + 3,2 + 2,6 + 2,7 K4 0 + 2,7 + 3,0 + 3,7 + 5,8 + 4,6 K2 0 + 1,6 + 2,3 + 3,2 + 4,8 + 5,1 The washing tests were carried out in the Linitestgerät at 40 ° C; Washing time 30 min. 1.5 g / l WMP were pre-dissolved in 200 ml water (15 ° dH) and 0.5 g / l sodium perborate monohydrate was added. Before the start of the washing tests, 0; 1.5; 3; 6; 12; 25 mg / l of the catalysts added. The washing tests were carried out analogously to Example 3. The table shows the reflectance differences ΔRE of the washes with and without a catalyst. catalyst Catalyst concentration [mg / l] 0 1.5 3rd 6 12th 25th K1 0 + 2.0 + 2.0 + 3.2 + 2.6 + 2.7 K4 0 + 2.7 + 3.0 + 3.7 + 5.8 + 4.6 K2 0 + 1.6 + 2.3 + 3.2 + 4.8 + 5.1

Die Ergebnisse zeigen, daß die erfindungsgemäßen Katalysatoren bereits in geringsten Konzentrationen eine deutliche Verstärkung der Bleichleistung von Wasserstoffperoxid bewirken.The results show that the catalysts according to the invention significantly increase the bleaching performance of hydrogen peroxide even in the lowest concentrations.

Beispiel 6: Konzentrationsabhängigkeit der katalysierten Peressigsäure-BleicheExample 6: Concentration dependence of the catalyzed peracetic acid bleach

Die Versuche wurden analog Beispiel 5 durchgeführt. Zusätzlich wurden jeweils 0,25 g/l TAED zur Waschlauge hinzugegeben. In der folgenden Tabelle sind die jeweiligen Remissionsdifferenzen ΔRE der Wäschen mit und ohne Katalysator aufgeführt. Katalysator Katalysator-Konzentration [mg/l] 0 1,5 3 6 12 K1 0 + 1,6 + 2,2 + 3,0 + 3,3 K4 0 + 1,6 + 2,6 + 1,5 + 0,7 K2 0 + 2,4 + 2,8 + 4,5 + 5,4 The tests were carried out analogously to Example 5. In addition, 0.25 g / l TAED was added to the wash liquor. The table below shows the respective reflectance differences ΔRE of the washes with and without a catalyst. catalyst Catalyst concentration [mg / l] 0 1.5 3rd 6 12th K1 0 + 1.6 + 2.2 + 3.0 + 3.3 K4 0 + 1.6 + 2.6 + 1.5 + 0.7 K2 0 + 2.4 + 2.8 + 4.5 + 5.4

Die Ergebnisse zeigen, daß die erfindungsgemäßen Katalysatoren bereits in geringsten Konzentrationen eine deutliche Verstärkung der Bleichleistung von Peressigsäure bewirken.The results show that the catalysts according to the invention bring about a significant increase in the bleaching performance of peracetic acid even in the lowest concentrations.

Beispiel 7: Einfluß verschiedener Oxidationsmittel auf das BleichergebnisExample 7: Influence of various oxidizing agents on the bleaching result

Die Waschversuche wurden im Linitestgerät bei 20°C durchgeführt.

Wasserhärte:
15°dH
Waschzeit:
30 min
Anschmutzung:
Tee auf Baumwolle (BC-1)
Waschmittel:
1,5 g/l WMP-Waschmittel
The washing tests were carried out in the Linitest at 20 ° C.
Water hardness:
15 ° dH
Washing time:
30 min
Soiling:
Tea on cotton (BC-1)
Laundry detergent:
1.5 g / l WMP detergent

Oxidationssysteme:

PAP:
Phthalimidoperoxicapronsäure (0,5 g/l)
BOBS:
Benzoyloxybenzolsulfonat-Natrium (0,25 g/l) in Kombiantion mit 0,5 g/l Natriumperborat-Monohydrat
Caroat:
Kaliumperoxomonosulfat (0,5 g/l)
Oxidation systems:
PAP:
Phthalimidoperoxicaproic acid (0.5 g / l)
BOBS:
Benzoyloxybenzenesulfonate sodium (0.25 g / l) in combination with 0.5 g / l sodium perborate monohydrate
Caroat:
Potassium peroxomonosulfate (0.5 g / l)

In der folgenden Tabelle sind die jeweiligen Remissionsdifferenzen ΔRE der Wäschen mit und ohne Katalysator aufgeführt. Katalysator Oxidationsmittel PAP BOBS Caroat K1 ohne +7,1 + 6,0 + 3,2 mit + 9,2 + 6,5 + 5,8 K4 ohne + 7,6 + 6,5 + 3,7 mit + 9,1 + 7,2 + 5,6 K2 ohne + 7,0 + 5,9 + 3,1 mit + 9,0 + 8,8 + 6,7 The table below shows the respective reflectance differences ΔRE of the washes with and without a catalyst. catalyst Oxidizing agent PAP BOBS Caroat K1 without +7.1 + 6.0 + 3.2 With + 9.2 + 6.5 + 5.8 K4 without + 7.6 + 6.5 + 3.7 With + 9.1 + 7.2 + 5.6 K2 without + 7.0 + 5.9 + 3.1 With + 9.0 + 8.8 + 6.7

Die Ergebnisse zeigen, daß die Katalysatoren bereits in geringsten Konzentrationen in der Lage sind, die Bleichleistung verschiedenartiger Oxidationsmittel bei 20°C zu steigern.The results show that the catalysts are able to increase the bleaching performance of various types of oxidizing agents at 20 ° C even in the smallest concentrations.

Claims (9)

Bleichmittelsysteme enthaltend enthaltend Bis- und Tris-(µ-oxo)-di-Mangan-Komplexsalze der Formel I

        [LMn(µ-O)a(µ-OAc)bMnL]xAy     (I)

worin Ac   eine C2-C8-Acylgruppe ist, a   ist 1, 2 oder 3, b   ist 0, wenn a 2 oder 3 ist oder b ist 2, wenn a 1 ist, x   bezeichnet die Anzahl der positiven Ladungen und ist 2 oder 3, A   ist ein ein- oder zweifach negativ geladenes Anion, y   bedeutet die für den Ausgleich der positiven Ladungen erforderliche equivalente Menge an Anion A und L   bedeutet einen Liganden der Formel II
Figure imgb0004
 worin R C1-C12-Alkyl, C5-C10-Cycloalkyl, Phenyl, NH2, NHR2, N(R2)2, OH, OR2 oder COOH, R1 Wasserstoff, C1-C12-Alkyl, C5-C10-Cycloalkyl, NH2, NHR2, N(R2)2, OH, OR2, COOH, COOR2, Cl, Br, F oder CN, R2 C1-C12-Alkyl oder C5-C10-Cycloalkyl bedeuten, g 2 oder 3 und m und n Null oder eine ganze Zahl von 1 bis 4 ist. Bleaching agent systems containing bis- and tris (µ-oxo) -di-manganese complex salts of the formula I.

[LMn (µ-O) a (µ-OAc) b MnL] x A y (I)

wherein Ac is a C 2 -C 8 acyl group, a is 1, 2 or 3, b is 0 if a is 2 or 3 or b is 2 if a is 1, x denotes the number of positive charges and is 2 or 3, A is a single or double negatively charged anion, y means the equivalent amount of anion A and required to balance the positive charges L represents a ligand of formula II
Figure imgb0004
 wherein RC 1 -C 12 alkyl, C 5 -C 10 cycloalkyl, phenyl, NH 2 , NHR 2 , N (R 2 ) 2 , OH, OR 2 or COOH, R 1 is hydrogen, C 1 -C 12 alkyl , C 5 -C 10 cycloalkyl, NH 2 , NHR 2 , N (R 2 ) 2 , OH, OR 2 , COOH, COOR 2 , Cl, Br, F or CN, R 2 C 1 -C 12 alkyl or C 5 -C 10 cycloalkyl, g is 2 or 3 and m and n is zero or an integer from 1 to 4. Bleichmittelsysteme nach Anspruch 1, dadurch gekennzeichnet, daß sie Verbindungen der Formel I enthalten, worin alle Substituenten R1 in den Liganden L Wasserstoff bedeuten und n = 1 ist.Bleaching agent systems according to Claim 1, characterized in that they contain compounds of the formula I in which all the substituents R 1 in the ligands L are hydrogen and n = 1. Bleichmittelsysteme nach Anspruch 1, dadurch gekennzeichnet, daß sie Verbindungen der Formel I enthalten, worin L einen Liganden der Formel II bedeutet und R C1-C4-Alkyl ist.Bleaching agent systems according to Claim 1, characterized in that they contain compounds of the formula I in which L is a ligand of the formula II and is RC 1 -C 4 -alkyl. Bleichmittelsysteme nach Anspruch 1, dadurch gekennzeichnet, daß sie Verbindungen der Formel I enthalten, wobei A Cl-, Br-, J-, NO3 -, ClO4 -, NCS-, PF6 -, RSO3 -, RSO4 -, SO4 2-, BPh4 -, OAc-.Bleaching agent systems according to Claim 1, characterized in that they contain compounds of the formula I, where A is Cl - , Br - , J - , NO 3 - , ClO 4 - , NCS - , PF 6 - , RSO 3 - , RSO 4 - , SO 4 2- , BPh 4 - , OAc - . Bleichmittelsysteme nach Anspruch 1, dadurch gekennzeichnet, daß ein anorganisches Peroxid aus der Gruppe der Percarbonate, Perborate, Perphosphate, Persilikate oder Peroxymono- oder disulfate enthalten.Bleaching agent systems according to Claim 1, characterized in that they contain an inorganic peroxide from the group of the percarbonates, perborates, perphosphates, persilicates or peroxymono- or disulfates. Bleichmittelsysteme nach Anspruch 1, dadurch gekennzeichnet, daß sie zusätzlich einen Bleichaktivator aus der Gruppe der reaktiven Ester, amide, Imide, Anhydride oder Nitrile enthält.Bleaching agent systems according to claim 1, characterized in that it additionally contains a bleach activator from the group of reactive esters, amides, imides, anhydrides or nitriles. Bleichmittelsysteme nach Anspruch 1, dadurch gekennzeichnet, daß sie den Bleichkatalysator in granulierter Form enthalten.Bleaching agent systems according to claim 1, characterized in that they contain the bleaching catalyst in granular form. Bleichmittelsysteme nach Anspruch 1, dadurch gekennzeichnet, daß sie den Bleichkatalysator als Bestandteil eines Bleichaktivatorgranulates enthalten.Bleaching agent systems according to claim 1, characterized in that they contain the bleaching catalyst as part of a bleach activator granulate. Wasch- und Reinigungsmittel enthaltend ein Bleichmittelsystem gemäß Anspruch 1.Detergents and cleaning agents containing a bleach system according to claim 1.
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WO2013060708A1 (en) 2011-10-25 2013-05-02 Basf Se Use of comb or block copolymers as soil antiredeposition agents and soil release agents in laundry processes
WO2014154508A1 (en) 2013-03-27 2014-10-02 Basf Se Block copolymers as soil release agents in laundry processes
US9790452B2 (en) 2013-03-27 2017-10-17 Basf Se Block copolymers as soil release agents in laundry processes
US10214606B2 (en) 2013-11-27 2019-02-26 Basf Se Random copolymers as soil release agents in laundry processes
WO2017186480A1 (en) 2016-04-26 2017-11-02 Basf Se Metal free bleaching composition

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EP0783035B1 (en) 2003-09-24
DE19600159A1 (en) 1997-07-10
US5942152A (en) 1999-08-24
ATE250660T1 (en) 2003-10-15
JPH09194886A (en) 1997-07-29
ES2207663T3 (en) 2004-06-01
EP0783035A3 (en) 1998-02-25
CA2194342A1 (en) 1997-07-05

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