WO2006024434A1

WO2006024434A1 - Diethyl methyl ammonium nitriles and detergents and cleaning agents containing said ammonium nitriles

Info

Publication number: WO2006024434A1
Application number: PCT/EP2005/009118
Authority: WO
Inventors: Gerd Reinhardt; Georg Borchers; Lars Cuypers; Ekaterina Jonas; Alexander Lerch; Michael Seebach
Original assignee: Clariant Produkte (Deutschland) Gmbh
Priority date: 2004-08-28
Filing date: 2005-08-24
Publication date: 2006-03-09
Also published as: DE102004041760A1; JP2008511701A; EP1784385A1; US20070245498A1

Abstract

The invention relates to diethyl methyl ammonium nitriles of formula (1), in which A represents an anion. Said compounds are suitable for use as bleach activators in detergents and cleaning agents.

Description

Diethylmethyl ammonium nitriles and detergents and cleaners containing these ammonium nitriles

This invention relates to odorless short chain ammonium nitriles, their granules, and their use for enhancing the bleaching effect of peroxygen compounds in bleaching colored stains on textiles as well as on hard surfaces, as well as detergents and cleaners containing these nitriles as bleach activators.

Inorganic peroxygen compounds, particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes. The oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with hydrogen peroxide or perborate in alkaline bleaching liquors only at temperatures above about 80 ⁰ C, a sufficiently fast bleaching of soiled textiles.

It is known that the oxidation effect of peroxidic bleaches, such as perborates, percarbonates, persilicates and perphosphates, can be improved at low temperatures by adding precursors of bleaching peroxyacids, so-called bleach activators. Many substances are known in the art as bleach activators. These are usually reactive organic compounds having an O-acyl or N-acyl group which in alkaline solution together with a source of hydrogen peroxide form the corresponding peroxyacids. Representative examples of bleach activators include N, N, N \ N'-tetraacetylethylenediamine (TAED), glucose pentaacetate (GPA), xylose tetraacetate (TAX), sodium 4-benzoyloxybenzenesulfonate (SBOBS), sodium trimethylhexanoyloxybenzenesulfonate (STHOBS), tetraacetylglycoluril (TAGU). , 1-phenyl-3-acetylhydantoin (PAH), sodium nonanoyloxy-benzenesulfonate (NOBS) and sodium isononanoyloxy-benzenesulfonate (ISONOBS). An interesting group is cationic compounds containing a quaternary ammonium group, since they are highly effective bleach activators.

By adding these activators to an aqueous peroxide solution, perhydrolysis occurs to release an organic peracid. As a result, the bleaching effect of the solutions is increased so much that they have at temperatures between 40 and 60 ⁰ C essentially the same effects as a peroxide solution alone at 95 ⁰ C.

A major drawback of said bleach activators is that they mostly leave large volume leaving groups (e.g., phenolsulfonates) after perhydrolysis, which are of no importance to the bleaching process.

From an ecological point of view, therefore, bleach activators are of interest in which a highly reactive peracid but no leaving group is released in the perhydrolysis step. This is e.g. achieved by a cyano group. In perhydrolysis, this probably forms a peroxyimidic acid, which then acts as a bleaching agent.

Examples include ammonium nitriles, characterized by the structural element

Compounds of this type and their use as activators in bleaching agents are described in EP-A-303 520, EP-A-458 396 and EP-A-464 880. Ammonium nitriles, where two of the groups R ¹ , R ² or R ^{3 is} a long-chain Alkyl group are claimed in WO 03/078561. However, of particular interest are low molecular weight ammonium nitriles with a total of not more than 12 carbon atoms, as they are excellent water-soluble, highly reactive and at the same time particularly weight-effective. The latter plays a special role in volume-effective detergents with low dosage. There has therefore been no shortage of attempts to make such compounds in the past. Numerous patent applications therefore describe the use of trimethylammonium acetonitriles of the formula

where X ^"is an anion, for example chloride, sulfate, hydrogensulfate, methylsulfonate, ethanesulfonate, toluenesulfonate, benzenesulfonate or cumene sulfonate Examples of synthesis, granulation and use of these trimethylammonium acetonitriles can be found in WO 02/012175, WO 02/012427, DE 100 38 844 or EP 13 12 665.

A serious disadvantage of all trimethylammonium acetonitriles, however, is that under alkaline conditions, whether in the wash liquor or prolonged storage in an alkaline detergent, they release traces of trimethylamine and thus a fishy odor, which makes their use in the household area impossible. There has therefore been no lack of attempts to produce odorless trimethylammonium acetonitriles, for example by replacement of the anion or by deodorization, as described in DE 102 24 509.

Surprisingly, the higher homologue (dimethylethylammonium acetonitrile tosylate) also releases traces of trimethylamine under alkaline conditions. By alkaline treatment, traces of trimethylamine can be detected even from N-methylmorpholinium acetonitrile methosulfate. The mechanism of formation is unclear, but it is likely that one of the nitrogen groups bound to ammonia transferred, which is released by hydrolysis of the nitrile. Repeated methyl group transfer then forms traces of trimethylamine.

Surprisingly, it has now been found that N-methyl-ammonium nitriles of the type described above, which have two ethyl substituents, are effective bleach activators which do not form trimethylamine under alkaline conditions, even though one methyl group is still on the nitrogen.

The present invention thus relates to compounds of the general formula

where X ^"is an anion, for example chloride, bromide, sulfate, hydrogensulfate, methosulfonate, ethanesulfonate, toluenesulfonate, benzenesulfonate or cumene sulfonate, particularly preferably the anions chloride, hydrogensulfate, sulfate, methosulfate and toluenesulfonate.

By means of some general examples, the synthesis routes for the diethylmethylammonium acetonitriles of this invention are shown:

1. Diethylamine is presented together with a base, preferably alkali metal carbonate or alkali metal hydroxide, in a solvent, preferably in absolute ethanol or in a toluene / water mixture. At temperatures between 0 and 5O ⁰ C, preferably at 10 to 30 ⁰ C, chloroacetonitrile is added dropwise. After 1 to 50 hours reaction time, the organic phase is separated and the aqueous phase extracted with an organic solvent. From the combined organic phases, the solvent is removed. The crude product obtained can be further purified by fractional distillation. The resulting diethylaminoacetonitrile is taken up in water or an organic solvent and with an alkylating agent such as methyl chloride, dimethyl sulfate or p-toluenesulfonate at temperatures between 20 and 100 ⁰ C to the corresponding N-cyanomethyl-ammonium Sa! z reacted. The salt can be recovered by conventional methods of workup such as extraction, crystallization, suction filtration, washing of the crystal slurry on the filter and drying. Analog can be assumed to be ethylmethylamine, wherein the quaternization is then carried out with an ethyl derivative.

2. Diethylmethylamine and chloroacetonitrile are reacted in a suitable solvent, for example in acetone for 1 to 12 hours at temperatures between 10 and 70 ⁰ C. The resulting precipitate, the N-cyanomethyl-ammonium chloride is filtered off, washed with an organic solvent and dried.

3. Diethylamine, sodium cyanide and an aldehyde or a ketone, preferably formaldehyde in the form of a 36% formalin solution, are combined in a solvent, preferably an ethanol / water mixture or water. After a reaction time of 1 to 12 hours at temperatures between 10 and 80 ⁰ C, preferably at 10 to 30 ⁰ C aqueous hydrochloric acid is added to the approach. The aqueous phase is extracted with a suitable organic solvent, for example methylene chloride or diethyl ether. From the combined organic phases, the solvent is stripped off after drying over magnesium sulfate. The crude product obtained can be further purified by fractional distillation. The resulting dialkylaminoacetonitrile is taken up in an organic solvent and reacted with an alkylating agent such as methyl chloride, dimethyl sulfate or Arylsulfonsäurealkylester at temperatures between 20 and 100 ⁰ C to the corresponding N-cyanomethyl-ammonium salt. The salt can be recovered by conventional methods of workup such as extraction, crystallization, suction filtration, washing of the crystal slurry on the filter and drying. Analog can be assumed that ethylmethylamine be carried out, wherein the quaternization is then carried out with an ethyl derivative.

The invention also provides the use of these ammonium nitriles as bleach activators in bleaching detergents and cleaners. In a particular embodiment, the diethylmethylammonium acetonitrile according to the invention is used in the form of granules in detergents and cleaners. Such granules may contain from 5 to 95% by weight, but preferably from 20 to 90% by weight, of the diethylmethylammonium acetonitrile according to the invention. As further constituents, such granules may contain a further bleach activator. Preference is given here to decanoyloxybenzoic acid, nonanoyloxybenzenesulfonate sodium, tetraacetylethylenediamine or 1,5-diacetyl-2,4-dioxo-1,3,5-hexahydrotriazine. In addition, granulation aids and / or coating materials can be used to construct the granules.

The term bleaching is understood here to mean both the bleaching of dirt located on the textile surface and the bleaching of dirt located in the wash liquor and detached from the textile surface. For bleaching on hard surfaces

Soiling applies mutatis mutandis the same. Further potential applications can be found in the Personal Gare area e.g. in the bleaching of hair and to improve the effectiveness of denture cleaners. Furthermore, the complexes according to the invention find use in commercial laundries, in wood and paper bleaching, bleaching of cotton and in disinfectants.

Furthermore, the invention relates to a process for the purification of textiles as well as hard surfaces, in particular dishes, using said cationic nitriles in aqueous, optionally further detergent or cleaning agent components, in particular oxidizing agents

Peroxygen base, containing solution, and detergents and hard surface cleaners, in particular, dishwashing detergents, and such are preferred for use in machine processes containing such cationic nitriles.

The use according to the invention consists essentially in creating conditions under which a peroxidic oxidizing agent and the cationic nitrile can react with one another in the presence of a hard surface contaminated with colored stains or a correspondingly soiled textile, with the aim of obtaining more strongly oxidizing secondary products. Such conditions are especially present when the reactants meet in aqueous solution. This can be done by separately adding the peroxygen compound and the cationic nitrile to an optionally washing or cleaning agent-containing solution. However, the process according to the invention is particularly advantageously carried out using a detergent or hard surface cleaning agent according to the invention which contains the cationic nitriles and optionally a peroxygen-containing oxidizing agent. The peroxygen compound may also be added to the solution separately, in bulk or as a preferably aqueous solution or suspension, when a non-oxygen detergent or cleaner is used.

The detergents and cleaners according to the invention, which may be in the form of granules, powdered or tablet-like solids, other shaped articles, homogeneous solutions or suspensions, may contain, in addition to the said bleach-enhancing active substance and a peroxygen compound, in principle all known ingredients customary in such agents. The compositions according to the invention may contain, in particular, builder substances, surface-active surfactants, peroxygen compounds, additional peroxygen activators or organic peracids, water-miscible organic solvents, sequestering agents, thickeners, preservatives, pearlescers, emulsifiers and enzymes, as well as special additives with color or fiber-sparing action. Other excipients such as electrolytes, pH Regulators, silver corrosion inhibitors, foam regulators as well as dyes and fragrances are possible.

Suitable peroxygen compounds are hydrogen peroxide and hydrogen peroxide donating under the conditions of washing and purification

Compounds such as alkali metal peroxides, organic peroxides such as urea-hydrogen peroxide adducts and inorganic persalts, such as alkali metal perborates, percarbonates, perphosphates, persilicates, persulfates and peroxynitrite. Mixtures of two or more of these compounds are also suitable. Particularly preferred are sodium perborate tetrahydrate and in particular sodium perborate monohydrate and sodium percarbonate. Sodium perborate monohydrate is preferred for its good storage stability and good solubility in water. Sodium percarbonate may be preferred for environmental reasons. Alkali hydroperoxides are another suitable group of

Peroxide compounds. Examples of these substances are cumene hydroperoxide and t-butyl hydroperoxide.

Aliphatic or aromatic mono- or dipercarboxylic acids and the corresponding salts are suitable as peroxy compounds. Examples are peroxynaphthoic acid, peroxylauric acid, peroxystearic acid,

N, N-phthaloylaminoperoxycaproic acid, 1,12-diperoxydodecanedioic acid, 1, 9-diperoxyazelaic acid, diperoxysebacic acid, diperoxyisophthalic acid, 2-decyldiperoxybutane-1,4-diacid and 4,4'-sulfonyl-bisperoxybenzoic acid.

In such detergents and cleaning agents, the cationic, nitrile bleach activator according to the invention may be present in a proportion by weight of about 0.1 to 20%, preferably of 0.5 to 10%, in particular of 0.5 to 5.0%, together with a peroxy compound. The proportion by weight of this peroxy compound is usually from 2 to 40%, preferably from 4 to 30%, especially from 10 to 25%. In addition to the cationic, nitrile bleach activators according to the invention, other suitable bleach activators may be present in the detergents and cleaners in the usual amounts (about 1 to 10% by weight). Suitable bleach activators are organic compounds with an O-acyl or

N-acyl group, in particular from the group of the activated carboxylic acid esters, in particular sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxybenzenesulfonate, sodium 4-benzoyloxy-benzenesulfonate, sodium trimethylhexanoyloxy-benzenesulfonate, carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, lactones, acylals, carboxylic acid amides, acyl lactams, acylated ureas and oxamides, N-acylated hydantoins, for example 1-phenyl-3-acetylhydantoin, hydrazides, triazoles, hydrotriazines, Urazoles, diketopiperazides, sulphurylamides, polyacylated alkylenediamines, for example NNN'.N'-tetraacetylethylenediamine, acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, acylated glycolurils, in particular tetraacetylglycoluril, N- Acylimides, in particular N-nonaoylsuccinimide, and acylated sugar derivatives, in particular pentaacetylglucose (PAG), pent acetylated, optionally N-alkylated glucamine and gluconolactone and / or N-acylated lactams, for example N-benzoylcaprolactam, but also quaternary nitrile compounds, for example quaternary trialkylammonium nitrile salts as described in EP-A-303 520, EP-A No. 4,548,396 and EP-A-464 880, in particular the cyanomethyltrimethylammonium salt, but also heterocyclic substituted quaternary nitrile compounds, as described in EP-A-790 244.

In addition to or in place of the conventional bleach activators listed above, sulfonimines, open chain or cyclic quaternary iminium compounds such as dihydroisoquinolinium betaines, and / or other bleach-enhancing transition metal salts, or mono- or polynuclear transition metal complexes having acyclic or macrocyclic ligands can also be included. The detergents and cleaners may comprise one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants. Such surfactants are present in detergent compositions according to the invention in proportions of preferably from 1 to 50% by weight, in particular from 3 to 30% by weight, whereas in hard-surface cleaners normally lower proportions, that is to say amounts of up to 20% by weight , in particular up to 10 wt .-% and preferably in the range of 0.5 to 5 wt .-% are included. Dishwashing detergents typically use low-foam compounds.

Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups. As surfactants of the sulfonate type are preferably Cg-C-ia-alkylbenzenesulfonates, olefinsulfonates, that is mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained for example from monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates which are obtained from C 12 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of alpha-sulfo fatty acids (ester sulfonates), for example the alpha-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids obtained by sulfonating the methyl esters of fatty acids of plant and / or animal origin having 8 to 20 carbon atoms be prepared in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts.

Other suitable anionic surfactants are sulfated fatty acid glycerol esters, which are mono-, di- and triesters and mixtures thereof. Alk (en) yl sulfates are the alkali and especially the sodium salts of the Schwefelsäurehalbester C ₂ -C ₈ fatty alcohols are, for example, from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₈ -C ₂ o-oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis. 2,3-alkyl sulfates are also suitable anionic surfactants. Also suitable are the sulfuric acid monoesters of straight-chain or branched alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ -Cn alcohols having on average 3.5 moles of ethylene oxide (EO) or C ₁₂ -C ₈ -fatty alcohols 1 to 4 EO.

The preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ -C ₈ fatty alcohol residues or mixtures of these. Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosinate). As further anionic surfactants are in particular soaps, for example in amounts of 0.2 to 5 wt .-%, into consideration. Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.

The anionic surfactants, including the soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts. Anionic surfactants are preferably present in detergents according to the invention in amounts of from 0.5 to 10% by weight and in particular in amounts of from 5 to 25% by weight.

As nonionic surfactants are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used, in which the alcohol radical may be linear or preferably methyl branched in the 2-position, or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or Oleylaikohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C ₂ -C ₄ -alcohols with 3 EO or 4 EO, C 12 -n alcohols with 7 EO, C ₁₃ -C ₁₅ -alcohols with 3 EO ₁ 5 EO, 7 EO or 8 EO, C ₂ -C ₈ alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₂ -C ₄ alcohol containing 3 EO and Ci2-Ci ₈ linear alcohol with 7 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are (TaIg) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

The nonionic surfactants also include alkyl glycosides of the general formula RO (G) _x , in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and 6 for a Glycoside unit with 5 or 6 C-atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as a variable to be determined analytically, may also assume fractional values - between 1 and 10; preferably x is 1.2 to 1.4. Also suitable are polyhydroxy fatty acid amides of the formula (I) in which R ^{1 is} CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen; is an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups R ² R ⁴ -OR ⁵

I ^■ I

(I) R ¹ -CO-NZ (II) R ³ CO-NZ

The polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose. The group of polyhydroxy fatty acid amides also includes compounds of the formula (II) R ³ for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ⁴ for a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R ⁵ is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, preference being given to C 1 -C ₄ -alkyl or phenyl radicals, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain has at least two Is substituted hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group. [Z] is also obtained here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-alyloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl ester.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl N, N-dimethylamine oxide and N-tallow alkyl N, N-dihydroxyethyl amine oxide and the fatty acid alkanolamides may also be suitable. Other suitable surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. However, it is also possible to use gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides. Other surfactant types may have dendrimeric structures.

Suitable organic and inorganic builders are neutral or in particular alkaline salts which precipitate or complex calcium ions. Suitable and in particular ecologically harmless

Builders are crystalline, layered silicates of the general formula NaMSi ( _X ) O (2x + i), where M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1.9 to 4 and y for a Number from 0 to 33, for example Na-SKS-5 (O, -Na ₂ Si ₂ O ₅ ), Na-SKS-7 (P-Na ₂ Si ₂ O ₅ , natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ * H ₂ O), Na-SKS-10 (NaHSi ₂ O ₃ * 3H ₂ O, kanemite), Na-SKS-11 (T-Na ₂ Si ₂ O ₅₎ and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (5-Na ₂ Si ₂ O ₅ ) and finely crystalline, synthetic hydrous zeolites, in particular of the NaA type, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g. Zeolites and phyllosilicates may be included in an amount of up to 20% by weight on average.

Furthermore, non-neutralized or partially neutralized (co) polymeric polycarboxylic acids are suitable. These include the homopolymers of acrylic acid or methacrylic acid or their copolymers with other ethylenically unsaturated monomers such as acrolein, dimethylacrylic acid, ethylacrylic acid, vinylacetic acid, allylacetic acid, maleic acid, fumaric acid, itaconic acid, meth (allylsulfonic acid), vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid and phosphorous groups Monomers such as vinylphosphoric acid, allylphosphoric acid and acrylamidomethylpropanephosphoric acid and their salts, and hydroxyethyl (meth) acrylate sulfate, allyl alcohol sulfate and allyl alcohol phosphates.

Preferred (co) polymers have an average molar mass of from 1000 to 100 000 g / mol, preferably from 2000 to 75000 g / mol and in particular from 2000 to 35000 g / mol.

The degree of neutralization of the acid groups is advantageously from 0 to 90%, preferably from 10 to 80% and in particular from 30 to 70%.

Particularly suitable polymers include homopolymers of acrylic acid and copolymers of (meth) acrylic acid with maleic acid or maleic anhydride.

Other suitable copolymers are derived from terpolymers which are obtained by polymerization of 10 to 70 wt .-% of monoethylenically unsaturated dicarboxylic acids having 4 to 8 carbon atoms, their salts, 20 to 85 wt .-% monoethylenically unsaturated monocarboxylic acids having 3 to 10 C -Atoms or their salts, 1 to 50 wt .-% of monounsaturated monomers which release after hydrolysis hydroxyl groups on the polymer chain, and 0 to 10 wt .-% of other free-radically copolymerizable monomers.

Also suitable are graft polymers of monosaccharides, oligosaccharides, polysaccharides and modified polysaccharides and animal or vegetable proteins.

Preferred are copolymers of sugar and other polyhydroxy compounds and a monomer mixture of 45 to 96 wt .-% monoethylenically unsaturated C ₃ - to Cio-monocarboxylic acids or mixtures of C ₃ - to Cio-monocarboxylic acids and / or their salts with monovalent cations, 4 to 55 Wt .-% monoethylenically unsaturated

Monosulfonic acid-containing monomers, monoethylenically unsaturated sulfuric acid esters, vinylphosphoric acid esters and / or the salts of these acids with monovalent cations and 0 to 30 wt .-% of water-soluble unsaturated Compounds modified with 2 to 50 moles of alkylene oxide per mole of monoethylenically unsaturated compounds.

Other suitable polymers are polyaspartic acid or its derivatives in non-neutralized or only partially neutralized form.

Also particularly suitable are graft polymers of acrylic acid, methacrylic acid, maleic acid and other ethylenically unsaturated monomers to salts of polyaspartic acid, as usually obtained in the hydrolysis of the polysuccinimide described above. This can be dispensed with the otherwise necessary addition of acid for the preparation of only partially neutralized form of polyaspartic acid. The amount of polyaspartate is usually chosen so that the degree of neutralization of all incorporated in the polymer carboxyl groups does not exceed 80%, preferably 60%.

Further suitable builders are, for example, the carboxylic acids preferably used in the form of their sodium salts, such as citric acid, in particular trisodium citrate and trisodium citrate dihydrate, nitrilotriacetic acid and their water-soluble salts; the alkali metal salts of carboxymethyloxysuccinic acid, ethylenediaminetetraacetic acid, mono-, dihydroxy-succinic acid, α-hydroxypropionic acid, gluconic acid, mellitic acid, benzopolycarboxylic acids and those disclosed in U.S. Patent Nos. 4,144,226 and 4,146,495. Phosphate-containing builders, such as alkali metal phosphates, which may be in the form of their alkaline neutral or acidic sodium or potassium salts,. are suitable. Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen phosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with oligomerization amounts in the range of 5 to 1000, in particular 5 to 50, and mixtures of sodium and potassium salts. These builders may be contained from 5 to 80 wt .-%, preferably a proportion of 10 to 60 wt .-%.

The desired viscosity of the liquid agents can be achieved by adding water and / or organic solvents or by adding a combination of organic solvents and thickening agents.

In principle, all mono- or polyhydric alcohols are suitable as organic solvents. Alcohols having 1 to 4 carbon atoms, such as methanol, ethanol, propanol, isopropanol, straight-chain and branched butanol, glycerol and mixtures of the alcohols mentioned are preferably used. Further preferred alcohols are polyethylene glycols with a molecular weight below 2000. In particular, a use of polyethylene glycol having a molecular weight between 200 and 600 and in amounts up to

45 wt .-% and of polyethylene glycol having a molecular weight between 400 and 600 in amounts of 5 to 25 wt .-% are preferred. An advantageous mixture of solvents consists of monomeric alcohol, for example ethanol and polyethylene glycol in a ratio of 0.5: 1 to 1.2: 1.

Other suitable solvents include triacetin (glycerol triacetate) and 1-methoxy-2-propanol.

Preferred thickeners are hardened castor oil, salts of long-chain fatty acids, preferably in amounts of from 0 to 5% by weight and in particular in amounts of from 0.5 to 2% by weight, for example sodium, potassium, aluminum, magnesium and titanium stearates or the sodium and / or potassium salts of behenic acid, and polysaccharides, in particular xanthan gum, guar-guar, agar-agar, alginates and tyloses, carboxymethylcellulose and hydroxyethylcellulose, furthermore higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, Polyvinyl alcohol and polyvinylpyrrolidone and electrolytes such as sodium chloride and ammonium chloride used. Suitable thickeners are water-soluble polyacrylates which are, for example, cross-linked with about 1% of a polyallyl ether of sucrose and which have a relative molecular weight of above one million. Examples include under the name Carbopol ^® 940 and 941 polymers available. The crosslinked polyacrylates are used in amounts of not more than 1% by weight, preferably in amounts of from 0.2 to 0.7% by weight. The enzymes optionally contained in the agents according to the invention include proteases, amylases, pullulanases, cellulases, cutinases and / or lipases, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Durazym®, Purafect® OxP, Esperase® and / or Savinase®, amylases such as Termamy®, amylase-LT, Maxamyl®, Duramyl®,

Purafectel OxAm, cellulases such as Celluzyme®, Carezyme®, K-AC® and / or the cellulases and / or lipases known from international patent applications WO 96/34108 and WO 96/34092, such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®. The enzymes used can be adsorbed on carriers and / or embedded in encapsulants, as described, for example, in International Patent Applications WO 92/111347 or WO 94/23005, in order to protect them against premature inactivation. They are preferably present in detergents and cleaners according to the invention in amounts of up to 10% by weight, in particular from 0.05 to 5% by weight, enzymes which are particularly preferably stabilized against oxidative degradation being used.

Machine dishwashing detergents according to the invention preferably comprise the customary alkali carriers, for example alkali metal silicates, alkali metal carbonates and / or alkali hydrogen carbonates. The alkali carriers commonly used include carbonates, bicarbonates and alkali metal silicates having a molar ratio SiO ₂ / M ₂ O.

(M = alkali atom) from 1: 1 to 2.5: 1. Alkali silicates may be present in amounts of up to 40 wt .-%, in particular 3 to 30 wt .-%, based on the total agent. The alkali carrier system preferably used in cleaning agents according to the invention is a mixture of carbonate and

Hydrogen carbonate, preferably sodium carbonate and bicarbonate, which may be present in an amount of up to 50 wt .-%, preferably 5 to 40 wt .-%.

A further subject of the invention is a machine for cleaning dishes containing 15 to 65% by weight, in particular 20 to 60% by weight of water-soluble builder component, 5 to 25% by weight, in particular 8 to 17% by weight. Oxygen-based bleaching agents, respectively; based on the total agent, and 0.1 to 5 wt .-% of one or more of the above defined cationic nitrile activators. Such an agent is preferably low alkaline, that is its weight percent solution has a pH of 8 to 11, 5, in particular 9 to 11.

In a further embodiment of inventive means for the automatic cleaning of dishes are 20 to 60 wt .-% of water-soluble organic builder, in particular alkali citrate, 3 to 20 wt .-% alkali carbonate and 3 to 40 wt .-% Alkalidisilikat included.

To effect silver corrosion protection, silver corrosion inhibitors can be used in dishwashing detergents according to the invention. Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trihydric phenols, optionally alkyl- or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, titanium, zirconium, hafnium, molybdenum, vanadium or cerium salts and / or complexes.

If the agents foam too much during use, they may still contain up to 6% by weight, preferably about 0.5 to 4% by weight, of a foam-regulating compound, preferably from the group consisting of silicones, paraffins, paraffin-alcohol combinations , Hydrophobicized silicic acids, Bisfettsäureamide and mixtures thereof and other other known commercially available foam inhibitors are added. Preferably, the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamide are preferred. Further optional ingredients in the compositions according to the invention are, for example, perfume oils.

Among the organic solvents which can be used in the compositions according to the invention, especially if they are in liquid or pasty form, are alcohols having 1 to 4 C atoms, in particular methanol, ethanol, Isopropanol and tert-butanol, diols having 2 to 4 carbon atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compounds ethers. Such water-miscible solvents are preferably not present in the cleaning agents according to the invention

20 wt .-%, in particular from 1 to 15 wt .-%, present. In order to establish a desired pH, which does not naturally result from the mixture of the other components, the compositions according to the invention may contain system and environmentally acceptable acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid or alkali hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are preferably not more than 10% by weight, in particular from 0.5 to 6% by weight, in the compositions according to the invention.

Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, pentanediol or sorbic acid.

Suitable pearlescing agents are, for example, glycol distearate esters, such as ethylene glycol distearate, but also fatty acid monoglycol esters. Suitable salts or setting agents are, for example, sodium sulfate, sodium carbonate or sodium silicate (water glass).

As typical individual examples, for further additives sodium borate, starch, sucrose, polydextrose, RAED, stilbene compounds, methylcellulose, toluenesulfonate, cumene sulfonate, soaps and Siiicone be mentioned.

The compositions according to the invention are preferably in the form of pulverulent, granular or tablet-like preparations which compact in a manner known per se, for example by mixing, granulating, rolling and / or by spray-drying the thermally stable components and admixing the more sensitive components, in particular enzymes, bleaching agents and the bleach catalyst are to be expected, can be prepared. Solutions according to the invention in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.

For the production of particulate compositions having an increased bulk density, in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step known from the European patent specification EP 0 486 592 is preferred. Another preferred preparation by means of a granulation process is described in the European patent EP 0 642 576. The preparation of compositions according to the invention in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range from 800 to 1000 g / l can also be achieved by using the builder components with at least a proportion of liquid mixture components in a first process stage mixed with increasing the bulk density of this premix and subsequently - if desired, after an intermediate drying - the other constituents of the agent, including the cationic nitrile activator, combined with the thus obtained premix.

For the preparation of compositions according to the invention in tablet form, the procedure is preferably such that all components are mixed together in a mixer and the mixture is compressed by means of conventional tablet presses, for example Exzeriterpressen or rotary presses. This gives unbreakable, yet sufficiently rapidly soluble tablets under application conditions with flexural strengths of normally over 150 N. So preferably, a tablet produced in this way has a weight of 1-5 g to 40 g, in particular from 20 g to 30 g; at a diameter of 3-5 mm to 40 mm.

In addition to the ingredients already mentioned, the detergents and cleaners may contain any of the conventional additives in amounts commonly found in such compositions. Examples

Example 1: Synthesis of (Cyanomethyl) di-ethyl-methyl-ammonium chloride

17.4 g (0.2 mol) of N, N-diethylmethylamine were initially charged in 100 ml of acetone. 15.1 g (0.2 mol) were added dropwise to this solution at RT within 10 min.

Chloroacetonitrile, with the temperature rising to 27 ° C. After about 5 minutes, first precipitates were visible. The mixture is stirred at RT overnight, filtered from the product on the suction filter and washed with acetone. Subsequently, in the

Dryed vacuum oven. 20.4 g (0.125 mol, 63%) were obtained.

(CyanomethyO-di-ethyl-methyl ammonium chloride.

¹ H NMR: δ = 1.3 ppm (t, 6H, ethyl CH ₃ ); 3.2 (s, 3H, _N-CH3); 3.55 (q, 4H, ethyl

CH ₂ ); 5.15 (s, 2H, N-CH ₂ -CN).

Example 2:

Synthesis of (cyanomethyl) -di-ethyl-methyl-ammonium methosulfate

22.4 g (0.2 mol) of diethylaminoacetonitrile were initially charged in 100 ml of ethyl acetate. Within 10 min 25.2 g (0.2 mol) of dimethyl sulfate were added dropwise with ice cooling at an internal temperature of 10-15 ⁰ C. The

Reaction mixture was evaporated to dryness on a rotary evaporator (40 ⁰ C;

0.1 mbar). This gave 43.2 g (0.181 mol, 91%) (cyanomethyl) -di-ethyl-methyl ammonium methosulfate.

¹ H NMR: δ = 1.3 ppm (t, 6H, ethyl CH ₃ ); 3.1 (s, 3H, _N-CH3); 3.4 (s, 3H ₁ CH ₃ OSO ₃ ); 3.5 (q, 4H ₁ ethyl-CH ₂ ); 4.85 (s, 2H, N-CH ₂ -CN).

Example 3:

Synthesis of (cyanomethyl) -di-ethyl-methyl-ammonium tosylate 56.1 g (0.5 mol) of diethylaminoacetonitrile were dissolved in 75 ml of toluene and within 30 minutes a solution of 93.1 g (0.5 mol) of methyl tosylate added dropwise in 75 ml of toluene. The reaction mixture was stirred at reflux for 4 hours. The reaction mixture was cooled to room temperature and the precipitated solid filtered off. The filter cake was washed with 100 ml of toluene and the solid at 6O ⁰ C in vacuo. There were obtained 142.9 g (0.48 mol) of pure (cyanomethyl) -di-ethyl-methyl-ammonium tosylat, corresponding to a yield of 95.8%. Mp .: 115 ° C

¹ H-NMR (D ₂ O): δ = 7.65, (2H, d); δ = 7.32 (2H, d); δ = 4.59 (2H, s); δ = 3.51 (4H, q); δ = 3.14 (3H, s); δ = 2.35 (3H, s); δ = 1, 34 (6H, t)

Example 4: Production of a granulate

In a laboratory ploughshare mixer (type: Lödige M5R with knife head) 875 g (cyanomethyl) -di-ethyl-methyl-ammonium-tosylate powder were introduced and at a mixer speed of n = 100 min ^"1 to a temperature of T = 60 ⁰ C heated. upon reaching the target temperature, the mixer speed was raised to n = 250 min ^"1, the cutter head turned on and within 2 min, a quantity of 125 g of Genapol T-500 melt in the mixer are metered. (Genapol T-500 = Fettalokohololyglykolether - commercial product Clariant GmbH). The Genapol melt was heated to a temperature of T = 80 ⁰ C prior to dosing. The product mixture was after the entry of the total amount of melt still mixed for about 30 sec. And then emptied from the mixer.

For granulation, a laboratory ring bender (type: Schlüter PP 85) was used, which was equipped with a 1 mm die. Prior to granulation, the essential work areas, die and Koller, were preheated to a temperature of T = 60 ⁰ C. The product mixture from the ploughshare mixer was metered into the ring roller press at a rate of about 80-100 g / min, which operated at a speed of n = 300 min ^-1 The distance between roller and ring die was about 0.4 mm set the distance of the Abstreifermessers was adjusted mm to about 4 the noodle resulting granules had a temperature of approx. 65 - 70 ⁰ C and were cooled prior to further processing to room temperature the product was finally (on a laboratory sieve type Retsch AS 200.. control) to separate fines <400 microns and coarse fractions> 1600 microns from the target product P2005 / 009118

24

Pasta granules were present in a composition of 87.5% (cyanomethyl) -diethyl-methyl-ammonium tosylate and 12.5% Genapol T-500. Example 5:

Production of a Co-Granulate from TAED and (Cyanomethyl) -di-ethyl-methylammonium tosylate

In a laboratory mixer (type: Eirich R-02) were presented 0.92 kg of TAED powder, 0.92 kg (cyanomethyl) -di-ethyl-methyl-ammonium-tosylate powder and 0.16 kg of bentonite (eg Ikomont NA white - commercial product of the company S & B Industrial Minerals GmbH). The products were intensively mixed for 2 minutes at a mixing vessel speed of n = 32 min ^-1 (stage I) and a swirler speed of n = 750 min ^-1

The powder mixture thus prepared was then pressed in a roll Konnpaktor (type: Hosokawa-Bepex Pharmapaktor L 200/30 P). The speed of the rolls was in the range of about 4 - 8 min ^"1 and the speed of the screw plug was in the range of about 18 - 25 min ^{" 1} varied in order to achieve a sufficient compaction of the powder. The pressed pieces were then comminuted gently on a screen mill (type: Alexanderwerk SKM / NR), using a sieve insert with a mesh width of 1600 μm. and a speed of 33 min ^" .1 The comminuted product was finally fractionated on a laboratory sieve (type Retsch AS 200 control) in order to separate off fine particles <400 μm from the target product, the finished compact being in a composition of 46% TAED , 46% (cyanomethyl) -di-ethyl-methyl ammonium tosylate and 8% bentonite.

Example 6: Odor test

Each 100 g of washing powder (Ariel, Fa. Procter & Gamble) were filled into 250 ml glass bottles and added in each case 5 g of a Cyanomethylammoniumsalzes. Subsequently, the bottles were stored for 4 weeks at 40 ⁰ C. After this time, the smell of the washing powder was smelled by a test penny.

Cyanomethylammonium salt Odor assessment Cyanomethyltrimethylammonium chloride strongly fishy

Cyanomethyldimethylethylammonium tosylate weakly fishy

Cyanomethyldiethylmethylammonium tosyiat (according to Example 3) neutral

The cyanomethylammonium salt according to the invention has no fishy odor and is therefore suitable for use in commercial products.

Example 7 Analytical Detection of Trimethylamine Formed from Cyanomethylammonium Salts Under Alkaline Conditions.

A 100 mg sample of the cyanomethyl-ammonium-salts was dissolved in 100 μl_ water and 2 mL of a 20% sodium carbonate solution and subsequently stored for 16 hours at 7O ⁰ C. Subsequently, the content of the formed trimethylamine (TMA) was determined by gas chromatography.

Cyanomethylammonium salt TMA after reaction Cyanomethyltrimethylammonium tosylate 26 ppm

Cyanomethyl dimethylethyl ammonium tosylate 20 ppm Methyl morpholinium acetonitrile methosulfate 3 ppm

Cyanomethyl-diethylmethylammonium tosylate 0 ppm

Example 8:

Bleaching performance of cyanomethyl-trialkylammonium salts, the bleaching performance of the cyanomethyl-trialkylammonium salts was investigated in a Linitest apparatus (Fa. Extracted) at 40 ⁰ C. For this purpose, 5 g / l of a bleach-free basic detergent (WMP, WFK, Krefeld) and 0.5 g / l of sodium perborate monohydrate (Degussa) were dissolved in water of hardness grade 3. Subsequently, 100 mg / l activator was added. The washing time was 30 min. Curry, ketchup and tea on cotton served as bleaching test cloth (BC-4, 10T and BC-1, WFK Testgewebe GmbH, Krefeld). As a bleaching result, the remission difference, measured with an Elrepho apparatus, after washing compared to the unwashed fabric was evaluated. Remission difference (dR%)

Activator BC-4 10T BC-1

Cyanomethyltrimethylammonium tosylate 62.1 74.7 55.1

Cyanomethyl diethylmethylammonium tosylate 62.9 75.2 54.9

It can be seen that the bleach activator according to the invention (prepared according to Example 3) has a comparable bleaching action as the prior art (cyanomethyltrimethylammonium tosylate, prepared by reacting dimethylaminoacetonitrile with p-toluenesulfonic acid methyl ester).

Essentially the same results were obtained when replacing the sodium perborate with sodium percarbonate monohydrate ^0.

Claims

claims:

1. Diethylmethylammonium nitriles of the formula (1)

C ₂ H ₅

H ₃ CN CH ₉ CN A ^"

C ₂ H ₅ (1)

where A is an anion.

2. Compounds of formula 1 according to claim 1, characterized in that A chloride, bromide, sulfate, hydrogen sulfate, methosulfonate, ethanesulfonate,

Toluene sulfonate, benzenesulfonate or cumene sulfonate means.

3. Compounds of formula 1 according to claim 1, characterized in that A is chloride, hydrogen sulfate, sulfate, methosulfate, ethanesulfonate or toluenesulfonate.

4. washing and cleaning agent containing a compound of formula 1 according to claim 1.

5. washing and cleaning agent containing a compound of formula 1 according to claim 1 in the form of granules.

6. Use of the diethyl-ammonium nitriles of formula (1) according to claim 1 together with a peroxygen compound for bleaching.