EP0909810B1 - Use of aminonitrile-N-oxides as bleach activators - Google Patents

Description

It is known that the bleaching power of peroxidic bleaching agents, such as perborates, Percarbonates, persilicates and perphosphates can be improved so that the Uses bleaching action at lower temperatures, for example at or below 60 ° C, by adding the precursors of bleaching peroxyacids, often called Bleach activators are called.

Many substances are known in the art as bleach activators. Usually these are reactive organic compounds with a O-acyl or N-acyl group in alkaline solution together with a source form the corresponding peroxyacids for hydrogen peroxide.

Representative examples of bleach activators are, for example N, N, N ', N'-tetraacetylethylenediamine (TAED), glucose pentaacetate (GPA), Xylose tetraacetate (TAX), sodium 4-benzoyloxybenzenesulfonate (SBOBS), Sodium trimethylhexanoyloxybenzenesulfonate (STHOBS), tetraacetylglucoluril (TAGU), tetraacetylcyanoic acid (TACA), di-N-acetyldimethylglyoxin (ADMG) and 1-phenyl-3-acetylhydantoin (PAH). For example, on GB-A-836 988, GB-A-907 356, EP-A-0 098 129 and EP-A-0 120 591.

In the meantime, nitrile bleach activators have become more important because they are turn out to be extraordinarily bleaching active. These are probably connections in perhydrolysis a peroxyimidic acid, which is the bleaching agent.

Such nitrile bleach activators and their use as bleach activators in Bleaching agents are described, for example, in EP 303 520, GB 802 035, US 4,883,917, US 5 478 356, US 5 591 378, WO 9 606 912 and WO 9 640 661.

Surprisingly, it has now been found that aminonitrile N-oxides or thereof derived salts have a better bleaching effect than bleach activators according to the state of the art.

worin

R¹, R²

unabhängig voneinander substituierte oder unsubstituierte C₁-C₁₅-Alkyl-, Cycloalkyl- oder Arylreste bedeuten, die durch Fluor, Chlor, Brom, C₁-C₅-Alkoxy, C₁-C₅-Alkoxycarbonyl, Amino, Ammonium, Carboxyl, Cyano oder Cyanamino substituiert sein können, oder zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen Ring mit 4 bis 6 Kohlenstoffatomen bilden, der durch C₁-C₅-Alkyl, C₁-C₅-Alkoxy, C₁-C₅-Alkanoyl, Phenyl, Amino, Ammonium, Cyano, Cyanamino, Chlor oder Brom substituiert sein kann und wobei dieser Ring zusätzlich zum Stickstoffatom anstelle von -CH₂-Gruppen ein oder zwei Sauerstoffatome oder eine Gruppe

enthalten kann, worin R³ Wasserstoff, C₁-C₇-Alkyl oder Cycloalkyl, Phenyl oder C₇-C₉-Alkylaryl ist, und

A

für einen C₁-C₅-Alkylen-, einen C₅-C₁₀-Cycloalkylen- oder einen Arylenrest steht

als Bleichaktivatoren. Die Begriffe "Aryl" bzw. "Arylen" in der obigen Formel bedeuten vorzugsweise "Phenyl" bzw. "Phenylen".The invention thus relates to the use of aminonitrile-N-oxides of the general formula (1) or their salts,

wherein

R ¹ , R ²

independently substituted or unsubstituted C ₁ -C ₁₅ alkyl, cycloalkyl or aryl radicals which are substituted by fluorine, chlorine, bromine, C ₁ -C ₅ alkoxy, C ₁ -C ₅ alkoxycarbonyl, amino, ammonium, carboxyl, Cyano or cyanamino can be substituted, or together with the nitrogen atom to which they are attached, form a ring with 4 to 6 carbon atoms, which is represented by C ₁ -C ₅ alkyl, C ₁ -C ₅ alkoxy, C ₁ -C ₅ -alkanoyl, phenyl, amino, ammonium, cyano, cyanamino, chlorine or bromine may be substituted and this ring in addition to the nitrogen atom instead of -CH ₂ groups, one or two oxygen atoms or a group

may contain, wherein R ^{3 is} hydrogen, C ₁ -C ₇ alkyl or cycloalkyl, phenyl or C ₇ -C ₉ alkylaryl, and

A

represents a C ₁ -C ₅ alkylene, a C ₅ -C ₁₀ cycloalkylene or an arylene radical

as bleach activators. The terms "aryl" or "arylene" in the above formula preferably mean "phenyl" or "phenylene".

The aminonitrile-N-oxides to be used according to the invention also include their salts, for example those salts which are obtained, for example, by reacting the corresponding aminonitrile-N-oxide with acids such as, in particular, HCl, HBr, HF, H ₂ SO ₄ , H ₃ PO ₄ and others acidic phosphates, pyro-, meta- and poly-phosphoric acid, HBF ₄ , HPF ₆ , H ₂ CO ₃ , HNO ₃ -, citric acid, formic acid, R ⁴ SO ₄ H, R ⁴ SO ₃ H, R ⁴ COOH, where R ^{4 represents} a substituted or unsubstituted C ₁ -C ₂₁ alkyl or aryl radical can be obtained.

Aminonitrile N-oxides or their salts of the formula 1 are preferred, in which R ¹ and R ^{2 are} C ₁ -C ₄ -alkyl, in particular methyl, and A is phenylene. The aminonitrile N-oxides or the salts derived therefrom are easily accessible by reacting aminonitriles with oxidizing agents; Such reactions are described, for example, in J. Backes "Amine", Methods of Organic Chemistry (Houben-Weyl), D. Klamann (ed.) Vol. E 16d (1992), pp. 1235-1329 and the literature cited therein.

The invention also relates to the use of these bleach activators in bleaching detergents and cleaning agents as well as in paper and textile bleaching. The detergents and cleaning agents contain a peroxide compound and the bleach activator usually also surface-active compounds and other known ingredients.

Suitable peroxidic bleaching agents are alkali peroxides, organic peroxides such as Urea peroxide, and inorganic persalts, such as the alkali perborates, -percarbonates, -perphosphates, -persilicates and -persulfate. Mixtures of two or more of these compounds are also suitable. Particularly preferred are sodium perborate tetrahydrate and especially sodium perborate monohydrate. Sodium perborate monohydrate is because of its good shelf life and its good solubility in water preferred. Sodium percarbonate can be made Environmental reasons may be preferred. Alkyl hydroperoxides are another suitable group of peroxide compounds. Examples of these substances are Cumene hydroperoxide and tert-butyl hydroperoxide.

The nitrile agent according to the invention can be used in the washing and cleaning agents Bleach activator with a weight fraction of about 0.05% to 20%, preferably of 0.5% to 10%, especially 1% to 7.5%, be present together with a peroxide compound. The proportion by weight of these peroxide compounds is usually from 1% to 60%, preferably from 4% to 30%, in particular from 10% up to 25%.

In the detergents and cleaning agents, in addition to those according to the invention Bleach activators and other suitable bleach activators, e.g. TAED, Tetraacetylglycoluril, glucose pentaacetate, sodium nonanoyloxybenzenesulfonate, Benzoylcaprolactam or nitrile activators may be included. These additional Bleach activators can be present in an amount of 1 to 10% by weight.

The surfactant can be derived from natural products such as Soap, or is a synthetic compound from the group of anionic, non-ionic, amphoteric, zwitterionic or cationic surface-active Substances, or mixtures of these. There are many suitable substances commercially available, and are described in the literature, for example in "Surface active agents and detergents", Vol. 1 and 2, by Schwartz, Perry and Berch. The total proportion of surface-active compounds can be up to 50 % By weight, preferably 1% by weight to 40% by weight, in particular 4% by weight up to 25% by weight.

Synthetic anionic surfactants are common water-soluble alkali metal salts of organic sulfates and sulfonates with alkyl radicals from about 8 to 22 carbon atoms, the term "alkyl" being the Includes alkyl substituents of higher aryl groups.

Examples include sodium and ammonium alkyl sulfates, especially the sulfates obtained by sulfating higher (C ₈ -C ₁₈ ) alcohols; Sodium and ammonium alkylbenzenesulfonates with an alkyl radical from C ₉ to C ₂₀ , in particular linear secondary sodium alkylbenzenesulfonates with an alkyl radical from C ₁₀ to C ₁₅ ; Sodium alkyl glycerol ether sulfates, especially the esters of the higher alcohols derived from tallow and coconut oil; the sodium sulfates and sulfonates of the coconut fatty acid monoglycerides; Sodium and ammonium salts of the sulfuric acid esters of higher (C ₉ to C ₁₈ ) oxalkylated, especially the fatty alcohols alkoxylated with ethylene oxide; the reaction products of the esterification of fatty acids with isethionic acid and subsequent neutralization with sodium hydroxide; Sodium and ammonium salts of the fatty acid amides of methyl taurine; Alkane monosulfonates such as those from the reaction of α-olefins (C ₈ -C ₂₀ ) with sodium bisulfite and those from the reaction of paraffins with SO ₂ and Cl ₂ with subsequent basic hydrolysis, giving a mixture of different sulfonates; Sodium and ammonium dialkyl sulfosuccinates with alkyl radicals from C ₇ to C ₁₂ ; and olefin sulfonates which are formed in the reaction of olefins, in particular C ₁₀ - to C ₂₀ -α-olefins, with SO ₃ and subsequent hydrolysis of the reaction products. The preferred anionic detergents are sodium alkylbenzenesulfonates with alkyl radicals from C ₁₅ to C ₁₈ , and sodium alkyl ether sulfates with alkyl radicals from C ₁₆ to C ₁₈ .

Examples of suitable nonionic surface-active compounds, which are preferably used together with anionic surface-active compounds, are in particular the reaction products of alkylene oxides (usually ethylene oxide) with alkylphenols (alkyl radicals from C ₅ to C ₂₂ ), the reaction products generally 5 to 25 ethylene oxide (EO ) Units contained in the molecule; the reaction products of aliphatic (C ₈ to C ₁₈ ) primary or secondary, linear or branched alcohols with ethylene oxide, generally with 6 to 30 EO, and the addition products of ethylene oxide with reaction products of propylene oxide and ethylenediamine. Other nonionic surface active compounds are alkyl polyglycosides, long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulfoxides.

Amphoteric or zwitterionic surfactants can also be used can be used in the compositions according to the invention, but what is usually not desired because of its high cost. If amphoteric or zwitterionic compounds are used, so this usually happens in small amounts in compositions that are mainly anionic and contain nonionic surfactants.

Soaps can also be used in the compositions according to the invention, preferably in a proportion of less than 25% by weight. They are particularly suitable in small amounts in binary (soap / anionic surfactant) or in ternary mixtures together with nonionic or mixed synthetic anionic and nonionic surfactants. The soaps used are preferably the sodium salts, and less preferably the potassium salts of saturated or unsaturated C ₁₀ -C ₂₄ fatty acids, or mixtures thereof. The proportions of such soaps can be from 0.5% by weight to 25% by weight, smaller amounts from 0.5% by weight to 5% by weight are generally sufficient for foam control. Soap contents between about 2% and about 20%, especially between about 5% and about 10%, have a positive effect. This is especially the case in hard water, where the soap serves as an additional builder.

The detergents and cleaning agents generally also contain a builder. As Builders come into consideration: calcium binding substances, precipitants, calcium-specific Ion exchangers and their mixtures. Examples of calcium binders include alkali metal polyphosphates such as sodium tripolyphosphate; Nitrilotriacetic acid and its water-soluble salts; the alkali metal salts of Carboxymethyloxy succinic acid, ethylenediaminetetraacetic acid, Oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid and Polyacetal carboxylates as described in U.S. Pat. 4,144,226 and 4,146,495.

Examples of precipitants are sodium orthophosphate, sodium carbonate and Long chain fatty acid soaps.

Examples of ion exchangers specific for calcium are various types of water-insoluble, crystalline or amorphous Aluminum silicates, of which the zeolites are the best known representatives.

These builder substances can be present from 5% by weight to 80% by weight, a proportion of 10% by weight to 60% by weight is preferred.

In addition to the ingredients already mentioned, the washing and Detergents contain each of the conventional additives in amounts that one usually finds in such means. Examples of such additives are Foaming agents, such as alkanolamides, especially the monoethanolamides Palm kernel oil fatty acids and coconut fatty acids; foam-preventing substances such as alkyl phosphates and silicones; Graying inhibitors and the like Auxiliaries such as sodium carboxymethyl cellulose and alkyl or substituted alkyl cellulose ethers; Stabilizers such as ethylenediaminetetraacetic acid; softener for textiles; inorganic salts such as sodium sulfate; and, usually small Quantities, fluorescent substances, perfumes, enzymes such as proteases, cellulases, Lipases and amylases, disinfectants and dyes.

The bleach activators of this invention can be used in a variety of laundry and Detergents are used. These include laundry detergents, Textile bleach, surface cleaners, toilet cleaners, Dishwasher cleaner, and also denture cleaner. The detergents can be in solid or liquid form. It is for the sake of stability and Manageability advantageous to the bleach activators in the form of granules use that contain a binder in addition to the bleaching catalyst. Various methods for producing such granules are in the patent literature described, for example, in Canada Pat. No. 1 102 966, GB-1 561 333, US-4 087 369, EP-A-0 240 057, EP-A-0 241 962, EP-A-0 101 634 and EP-A-0 062 523. Each of these methods is suitable for those according to the invention using aminonitrile-N-oxides applicable.

The granules containing the bleach activators are generally the Detergent composition along with the other dry Components such as enzymes, inorganic peroxide bleach added. The detergent composition to which the catalyst granules are added can be obtained in several ways, such as Dry mixing, extruding, spray drying.

In a further embodiment, the bleach activators according to the invention are Particularly suitable for non-aqueous, liquid detergents, together with a bleaching peroxide compound, such as sodium perborate, around the detergent great cleaning ability for fabrics and textiles. Not that aqueous, liquid detergents, pasty and gelatinous Including detergent compositions are well known in the art are known, and are described, for example, in US 2,864,770, US 2,940,938, US 4,772,412, US 3 368 977, GB-A-1 205 711 GB-A-1 370 377, GB-A-1 270 040, GB-A-1 292 352, GB-A-2 194 536, DE-A-2 233 771, EP-A-0 028 849.

These are compositions in the form of a non-aqueous, liquid medium in which a solid phase can be dispersed. Not that one aqueous, liquid medium can be a liquid, surface-active substance, preferably a nonionic surfactant; a non polar liquid medium such as liquid paraffin; a polar solvent such as Polyols, for example glycerin, sorbitol, ethylene glycol, possibly in combination with low molecular weight monohydric alcohols such as ethanol or isopropanol; or Mixtures of these.

The solid phase can consist of builder substances, alkalis, abrasive substances, Polymers and other solid ionic surfactants, bleaches fluorescent substances and other common solid ingredients.

The following non-exhaustive examples are intended to provide an overview of the Embodiments of the invention.

Example 1: Synthesis of para-dimethylaminobenzonitrile-N-oxide and the corresponding meta-chlorobenzoic acid salt

To dissolve 11.7 g para-dimethylaminobenzonitrile in 80 ml methylene chloride were at a temperature of 0 ° C to -5 ° C within two hours Solution of 13.8 g meta-chloroperoxybenzoic acid in 200 ml methylene chloride dropwise. After peroxide was no longer detectable (negative KI test) the solvent evaporated on a rotary evaporator. 25.7 g of para-dimethylaminobenzonitrile-N-oxide were obtained meta-Chlorbenzoesäuresalz. To Chromatography on alumina became pure para-dimethylaminobenzonitrile-N-oxide isolated.

bleaching tests

A lead composition was prepared by combining 200 ml of an aqueous solution of reference detergent WMP (laundry research Krefeld, 5 g / l in water with 15 ° dH) solution, 150 mg of sodium perborate monohydrate and 50 mg of the respective activator. With this composition, tissue pieces soiled with the standard soiling BC-1 tea (on cotton, laundry research Krefeld) were subjected to a treatment at a temperature of 40 ° C. under isothermal washing conditions in a Linitest device (Heraeus). After a thirty-minute washing time, the fabric pieces were rinsed with water, dried and ironed, then the bleaching effect was quantified by determining the differences ΔR _(AKT) in remission before and after bleaching using an ELREPHO 2000 whiteness measuring device (from Datacolor). From these ΔR _(AKT) values and the ΔR ₀ values determined in control experiments without bleach activator, the ΔΔR values listed in Table 1 were calculated, which represent a direct yardstick for the improvement in the bleaching effect caused by the addition of activator: ΔΔR = ΔR (ACT) - ΔR 0

1 2 3 4 5 ΔΔR 1,0 0,7 1,2 0,3 0,1 mCBA: meta-Chlorbenzoesäure-Salz Connections 1-5 are:

1 2 3 4 5 ΔΔR 1.0 0.7 1.2 0.3 0.1 mCBA: meta-chlorobenzoic acid salt

The washing experiments show that the aminonitrile N-oxides according to the invention have good bleaching performance.
Further advantageous properties of the complexes described are low color damage and low fiber damage.

Claims (8)

1. The use of aminonitrile N-oxides of the formula (1)

   

   in which

   R¹ and R²

   independently of one another are substituted or unsubstituted C₁-C₁₅-alkyl, cycloalkyl or aryl radicals which may be substituted by fluorine, chlorine, bromine, C₁-C₅-alkoxy, C₁-C₅-alkoxycarbonyl, amino, ammonium, carboxyl, cyano or cyanamino, or together with the nitrogen atom to which they are bonded form a ring having from 4 to 6 carbon atoms which may be substituted by C₁-C₅-alkyl, C₁-C₅-alkoxy, C₁-C₅-alkanoyl, phenyl, amino, ammonium, cyano, cyanamino, chlorine or bromine, which ring can contain, in addition to the nitrogen atom and instead of -CH₂- groups, one or two oxygen atoms or a group

   

   in which R³ is hydrogen, C₁-C₇-alkyl or cycloalkyl, phenyl or C₇-C₉-alkylaryl,

   A

   is a C₁-C₅-alkylene, a C₅-C₁₀-cycloalkylene or an arylene radical,

   as bleach activators in detergents and cleaners and also in paper and textile bleaching.
2. The use of aminonitrile N-oxides or salts thereof of the formula (1) as claimed in claim 1, wherein a compound of the formula (1) in which R¹ and R² are C₁-C₄-alkyl, in particular methyl, and A is phenylene is used.
3. A detergent or cleaner comprising a peroxide compound and an aminonitrile N-oxide of the formula (1) as claimed in claim 1.
4. A detergent or cleaner comprising a peroxide compound and from 0.05 to 20% by weight of an aminonitrile N-oxide of the formula 1 as claimed in claim 1.
5. A detergent or cleaner comprising from 1 to 60% by weight of a peroxide compound and an aminonitrile N-oxide of the formula (1) as claimed in claim 1.
6. A detergent or cleaner comprising an aminonitrile N-oxide of the formula (1) as claimed in claim 1 and a perborate, percarbonate, perphosphate, persilicate, monopersulfate, urea peroxide, cumene hydroperoxide or tert-butyl hydroperoxide.
7. A detergent or cleaner comprising a peroxide compound, an aminonitrile N-oxide of the formula (1) as claimed in claim 1 and a bleach activator which is not an aminonitrile N-oxide.
8. A detergent or cleaner comprising a peroxide compound, an aminonitrile N-oxide of the formula (1) as claimed in claim 1 and surface-active compounds.