US20030166484A1

US20030166484A1 - Coated, granular n-alkylammonium acetonitrile salts and use thereof as bleach activators

Info

Publication number: US20030166484A1
Application number: US10/381,204
Authority: US
Inventors: Arend Kingma; Axel Kistenmacher; Gregor Schurman; Michael Schonherr
Original assignee: Individual
Current assignee: BASF SE
Priority date: 2000-09-28
Filing date: 2001-09-28
Publication date: 2003-09-04

Abstract

The present invention relates to granular, coated N-alkylammoniumacetonitrile salts of the formula (I)

R²R³NR¹—CR⁴R⁵—CN⁺Y⁻ (I)

in which

R¹is a C₁-C₂₄-alkyl group which may be interrupted by nonadjacent oxygen atoms or may additionally carry hydroxyl groups, a C₄-C₂₄-cycloalkyl group, a C₇-C₂₄-alkaryl group or a group of the formula —CR⁴R⁵—CN,

R²and R³in each case independently of one another have the meaning of R¹or together are a saturated four- to nine-membered ring having at least one carbon atom and at least one further heteroatom from the group consisting of oxygen, sulfur and nitrogen,

R⁴and R⁵in each case independently of one another are hydrogen, a C₁-C₂₄-alkyl group which may be interrupted by nonadjacent oxygen atoms or may additionally carry hydroxyl groups, a C₄-C₂₄-cycloalkyl group or a C₇-C₂₄-alkaryl group and

Y is a sulfate or hydrogensulfate anion in the corresponding stoichiometric amount, which are coated with a material which is chosen from the group consisting of organic, inorganic, hydrophilic and hydrophobic substances.

Description

The present invention relates to N-alkylammoniumacetonitrile salts of the formula

R²R³NR¹—CR⁴R⁵—CN⁺Y⁻ (I)

in which R ¹to R⁶and Y have the meanings given in the text, which are in granular form and have been coated. The salts of the formula (I) are, because of their coating, highly suitable for use as bleach activators in, preferably, laundry and dishwashing detergents.

Bleach activators have been used in modem laundry and dishwashing detergents for some time. Here, they serve to activate the compounds customarily used as bleaches such that disintegration of these compounds is complete and/or takes place even at low temperatures, thus achieving the desired bleaching action.

There is a large number of classes of compound and compounds whose bleaching action toward very diverse substrates is known and which are therefore used as bleaches in a wide variety of detergents and cleaners, and generally in applications in the hygiene, personal care and industrial sector. In general, these are organic and inorganic peroxo compounds, frequently peroxo acids, and also perborates and percarbonates which are used in free form or in the form of the salts, preferably the alkali metal salts. Frequently, these peroxides do not disintegrate to the desired extent under the chosen conditions; for example, a temperature is often chosen for wash cycles which is insufficient to disintegrate the bleach. It has therefore proven necessary in practice to provide these compounds, when used in the known applications, with bleach activators, which bring about disintegration of the compounds used as bleaches and thus the bleaching action.

In practice, the bleach activators are frequently provided with a layer which surrounds them, as a result of which they are easier to dose and to handle, and often produce better washing results. Furthermore, in coated form, they are less likely to undergo hydrolysis, which in general readily occurs in the customary detergent and cleaner formulations because of the washing-active substances having an alkaline pH.

A known class of bleach activators are N-alkylammoniumacetonitrile salts of the formula

R²R³NR¹—CR⁴R⁵—CN⁺Y⁻ (I)

in which

R ¹is a C₁-C₂₄-alkyl group which may be interrupted by nonadjacent oxygen atoms or may additionally carry hydroxyl groups, a C₄-C₂₄-cycloalkyl group, a C₇-C₂₄-alkaryl group or a group of the formula —CR⁴R⁵—CN,

R ²and R³in each case independently of one another have the meaning of R¹or together are a saturated four- to nine-membered ring having at least one carbon atom and at least one further heteroatom from the group consisting of oxygen, sulfur and nitrogen,

R ⁴and R⁵in each case independently of one another are hydrogen, a C₁-C₂₄-alkyl group which may be interrupted by nonadjacent oxygen atoms or may additionally carry hydroxyl groups, a C₄-C₂₄-cycloalkyl group or a C₇-C₂₄-alkaryl group and

Y is a suitable anion.

This group of bleach activators is disclosed in the Patent Application EP-A 303 520 (Kao Corporation, earliest priority date 14.08.1987), WO 96/40661 (Clorox Company, priority date 07.06.1995) and the applications EP-A 790 244 (Hoechst AG, priority date 15.02.1996) and DE-A 197 40 669 (Clariant GmbH, filing date 17.09.1997). This latter application also describes the coating of the compounds with a suitable substance.

Although the nitrites disclosed in the applications cited in the paragraph above have excellent bleach activator properties, they are still burdened with certain disadvantages. For example, if the customarily used counterions Cl ⁻ or CH₃OSO₃ ⁻ are used, they are produced in a nongranular form which is generally difficult to process and difficult to dose, and the preparation of these salts is also involved, time-consuming and energy-intensive. There has therefore been no lack of attempts to convert these salts into an application-friendly form.

In the previously unpublished German application with the file reference 199 13 995.4 (filing date 29.03.1999), BASF AG describes a process which provides these nitrile salts in granular form. Here, the respective nitrile, which is in the form of the methylsulfate salt, is evaporated at a temperature of from 80 to 250° C. and a pressure of from 10 mbar to 2 bar to give a melt which is then left to solidify. During the evaporation, also thereafter, customary carrier materials and/or auxiliaries are added, and the resulting nitrile, which is in the form of the sulfate or hydrogensulfate, is converted to the crystalline state.

The process described above and disclosed in the German application with the file reference 199 13 995.4, and also the N-alkylammoniumacetonitrile salts obtainable thereby and of the formula (I) in which Y=HOSO ₃ ⁻ or SO₄ ²⁻ are an integral part of the present invention and are incorporated herein by reference.

The salts obtainable thereby, which are in principle highly suitable for use as bleach activators in detergents and cleaners and other applications containing bleaches, are, however, in need of improvement with regard to handling. As is the case for any chemical substance, it is necessary to avoid unnecessarily large amounts being taken up by people handling them. Particularly where the granules present are not abrasion-resistant, this is not ensured.

It is an object of the present invention to formulate the substances of the formula (I) in which R ¹to R⁶have the meanings given above and Y is an SO₄ ²⁻ ion or an HSO₃ ⁻ ion in a form which permits risk-free dealing with the substances, and at the same time to ensure simple handling.

We have found that this object is achieved by a granular, coated N-alkylammoniumacetonitrile salt of the formula (I)

R²R³NR¹—CR⁴R⁵—CN⁺Y⁻ (I)

in which

Y is a sulfate or hydrogensulfate anion in the corresponding stoichiometric amount,

where the salts of the formula (I) are coated with a material which is chosen from the group consisting of organic, inorganic, hydrophilic and hydrophobic substances.

The N-alkylammoniumacetonitrile salts of the formula (I) coated according to the invention are prepared by coating the granulates obtained following evaporation and conversion of the salts into a granular form corresponding to the process disclosed in the application with the file reference 199 13 995.4, in a manner known per se. The coating materials used are both inorganic and organic, and hydrophilic as well as hydrophobic substances.

Examples of organic, hydrophilic coating materials include fatty alcohols (also in a mixture with aluminum stearate), ethoxylated fatty alcohols and oxo alcohols, for example C ₈-C₃₁-fatty alcohol polyalkoxylates having 1 to 150 moles of ethylene oxide, fatty acids, for example lauric acid, myristic acid, stearic acid and the Na, K, Ca and ammonium salts thereof, fatty acid esters, waxes, for example paraffin waxes, montan ester wax, montan acid wax, polyethylene wax, oxidized polyethylene wax, ethylene/acrylic acid copolymer wax, ethylene/vinyl acetate copolymer wax, polyalkyl vinyl ether wax, dispersions of suitable polymers, for example of alkyl acrylate, styrene, alkyl acrylate/(meth)acrylic acid copolymers, maleic acid/olefin copolymers, vinyl chloride/ethylene copolymers, vinyl chloride/ethylene/methacrylate copolymers.

Examples of organic, hydrophilic coating materials include polyethylene glycols having a molecular weight of from 1 000 to 50 000, and also block copolymers and random copolymers of ethylene glycol and propylene glycol.

Examples of suitable inorganic coating materials include magnesium sulfate, sodium hexaphosphate, dihydrogen phosphate, pyrophosphate, phosphonic acids, sodium metaborate, sodium metasilicate, waterglass, sodium polyphosphate, sodium sulfate, sodium carbonate, sodium silicate, sodium bicarbonate, borax, magnesium sulfate and boric acid.

All of the coating materials listed above can be used alone or in a mixture with one or more other coating materials originating from the same group or from another group.

Suitable coating materials must have a melting point of ≧30° C., preferably ≧40° C., in particular ≧45° C.

Preference is given to using polyethylene glycols having a molecular weight of ≧1 500, long-chain fatty acids, fatty alcohol ethoxylates (for example of the Lutensol® type from BASF AG) and block copolymers of ethylene oxide and propylene oxide (for example of the Pluronic® type from BASF AG) as coating material.

In particular, polyethylene glycols having a molecular weight of about 6 000, fatty alcohol ethoxylates of the Lutensol® AT type from BASF AG (C ₁₆-C₁₈-fatty alcohol ethoxylates), ethylene oxide/propylene oxide block copolymers of the Pluronic® PE 6 800 type (ethylene oxide content about 80%, molecular weight about 8 000) and stearic acid are used as coating material.

Preferred substances of the formula (I) are those in which R ²and R³together with the nitrogen atom to which they are bonded form a six-membered ring, which may contain a further N atom or an oxygen atom, and also those in which R¹to R³are identical or different and are a C₁-C₄-alkyl radical. The most preferred substances according to the present invention are N-methylmorpholiniumacetonitrile sulfate or hydrogensulfate and trimethylammoniumacetonitrile sulfate and hydrogensulfate.

The coating can be applied from the melt or from solutions or dispersions, the solvent or emulsifier being removed by evaporation. Application as a fine powder, for example by electrostatic techniques, is also possible. Here, the coating materials can be applied to the granular N-alkylammoniumaetonitriles in stirring, mixing and granulation apparatuses. Preference is given to applying the coating materials in a fluidized bed, it being possible to simultaneously classify the size of the particles. Should the coating materials lead under certain circumstances to tacky products, it may be useful to additionally provide the coated granular N-alkylammoniumacetonitriles with finely divided substances (“dusting”). Suitable dusting agents are all finely divided substances, it also being possible to use other detergent constituents such as builder substances. Preference is given to using zeolites, silicates, polycarboxylates, carbonates, citrates and starch as additional dusting agents.

The amount of coating material used for the bleach activator used according to the invention is from 2 to 30% by weight, based on the base granulate containing the bleach activator.

Preferred amounts of coating material are from 5 to 20% by weight, in particular 5 to 15% by weight, in each case based on the base granulate.

Furthermore, it may be useful, in order to achieve an optimal coating, to deliberately maintain the temperature over a relatively long period in the region of the melting temperature during the coating process in order to achieve an improved coating.

The average particle size of the granular N-alkylammoniumacetonitrile coated according to the invention is in the range from 100 μm to 3 000 μm, preferably in the range from 300 μm to 2 000 μm, very particularly preferably 500 μm to 1 200 μm.

The granular N-alkylammoniumacetonitriles to be coated can also be coated or used in combination with other bleach activators. These are, for example, compounds which, under perhydrolysis conditions, produce aliphatic peroxocarboxylic acids having, preferably, 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid. The bleach activators frequently contain one or more N- or O-acyl groups and/or carry optionally substituted benzoyl groups, such as substances from the class of anhydrides, esters, imides and acylated imidazoles or oximes. Examples thereof are tetraacetylethylenediamine (TAED), tetraacetylmethylenediamine (TAMD), tetra-acetylglycoluril (TAGU), tetraacetylhexylenediamine (TAHD), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonates (n- or iso-NOBS) and lauroyloxybenzenesulfonates (LOBS), pentaacetylglucose (PAG), 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine (DADHT) and isotoic anhydride (ISA).

In combination with the granular N-alkylammoniumacetonitriles coated according to the invention, it is also possible to use bleach activators from the group consisting of carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and the enol esters known from the German Patent Applications DE 196 16 693 and DE 196 16 767, and also acetylated sorbitol and mannitol and mixtures thereof (SORMAN) described in European Patent Application EP 0 525 239, acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, and acetylated, optionally N-alkylated glucamine and gluconolactone, and/or N-acylated lactams, for example N-benzoylcaprolactam and carbonylbiscaprolactam, which are known from the International Patent Applications WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759, WO 95/17498 and WO 96/36686, and also bis(2-propyl-imino)carbonate, see DE-A 195 18 039, 195 41 012, 196 09 953 and 197 04 149.

Also suitable in combination with the granular N-alkylammoniumacetonitriles classed according to the invention are the hydrophilically substituted acylacetals known from the German Patent Application DE 196 16 769, and the acyllactams described in the German Patent Application DE 196 16 770 and International Patent Application WO 95/14075.

In addition to the conventional bleach activators listed above or instead of them, it is also possible to combine the sulfonimines known from the European Patent Specifications EP-A 0 446 982 and EP-A 0 453 003 and/or bleaching-boosting transition metal salts or transition metal complexes as so-called bleach catalysts with the granular N-alkylammoniumacetonitriles coated according to the invention. Suitable transition metal compounds include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum salene complexes known from German Patent Application DE 195 29 905 and the N-analogous compounds thereof known from German Patent Application DE 196 20 267, the manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes known from the German Patent Application DE 195 36 082, the manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes containing nitrogen-containing tripod ligands described in the German Patent Application DE 196 05 688, the cobalt, iron, copper and rutheniumammine complexes known from the German Patent Application DE 196 20 411, the manganese, copper and cobalt complexes described in German Patent Application DE 44 16 438, the cobalt complexes described in European Patent Application EP-A 0 272 030; the manganese complexes known from the European Patent Application EP-A 0 693 550, the manganese, iron, cobalt and copper complexes known from the European Patent Specification EP-A 0 392 592, and/or the manganese complexes described in European Patent Specification EP-B 0 443 651 or the European Patent Applications EP-A 0458 397, EP-A 0458 398, EP-A 0549 271, EP-A 0 549 272, EP-A 0 544 490 and EP-A 0 544 519.

In combination with the granular N-alkylammoniumacetonitriles coated according to the invention it is possible to choose bleaching-boosting transition metal complexes, in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and/or Ru, preferably chosen from the group of manganese and cobalt salts and complexes, particularly preferably cobalt (ammine) complexes, cobalt (acetate) complexes, cobalt (carbonyl) complexes, chlorides of cobalt and manganese and manganese sulfate. These bleaching-boosting transition metal complexes may be used in customary amounts, preferably in an amount up to 5% by weight, in particular from 0.0025% by weight to 1% by weight and particularly preferably from 0.01% by weight to 0.25% by weight, in each case based on the total cleaning formulation.

Preference is given to using polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), also glucose pentaacetate (GPA), xylose tetraacetate (TAX), sodium 4-benzoyloxybenzenesulfonate (SBOBS), sodium trimethylhexanoyloxybenzenesulfonate (STHOBS), tetraacetylglucoluril (TAGU), tetraacetylcyanic acid (TACA), di-N-acetyl-dimethylglyoxime (ADMG), 1-phenyl-3-acetylhydantoin (PAH), acylated phenolsulfonates, nonanoylbenzenesulfonates (NOBS), isononanoylbenzenesulfonates (isoNOBS), lauroylbenzenesulfonates (LOBS), carbonylbiscaprolactam and bis(2-propylimino)carbonate.

The coated, granular N-alkylammoniumacetonitriles according to the invention are generally used in combination with the bleaches listed below. Alkali metal perborates and their hydrates and alkali metal percarbonates, preference being given to using sodium perborate in the form of the mono- or tetrahydrate, or sodium percarbonate and hydrates thereof. It is also possible to use persulfates and hydrogen peroxide and typical oxygen bleaches, such as organic peracids, for example perbenzoic acid, peroxyalphanaphthoic acid, peroxylauric acid, peroxystearic acid, phthalimidoperoxycaproic acid, nonylimidoperoxysuccinic acid, nonylimidoperoxyadipic acid, 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelaic acid, diperoxoisophthalic acid and 2-decyldiperoxybutane-1,4-dioic acid. Also suitable are cationic peroxy acids, as are described in the patent applications U.S. Pat. No. 5,422,028, U.S. Pat. No. 5,294,362 and U.S. Pat. No. 5,292,447, and sulfonylperoxy acids, as are described, for example, in the patent application U.S. Pat. No. 5,039,447. Furthermore, the addition of small amounts of bleach stabilizers, such as, for example, phosphonates, borates, metaborates, metasilicates and magnesium salts may be useful.

The peroxy acid-containing bleach is used in amounts which produce an amount of available oxygen of between about 0.1% to about 10%, preferably between about 0.5% and about 5%, in particular from about 1% to 4%. The percentages are based on the total weight of the detergent composition.

The proportion of the peroxide-containing bleach in the detergent compositions according to the invention is between about 0.1% by weight and about 95% by weight and preferably about 1% by weight and about 60% by weight. If the bleach composition is also a completely formulated detergent composition, it is preferable for the proportion of peroxide-containing bleach to be between about 1% by weight and about 20% by weight.

The N-alkylammoniumacetonitriles coated according to the invention can also be used in combination with so-called bleaching performance boosters. These are substances which further increase the action of the known bleaches. Suitable bleach activators are, in particular, the diamines described in DE-A 196 11 992. These are compounds which contain secondary amine groups NHR ¹and which are of low molecular weight, oligomeric or polymeric. In particular, they are secondary amines of the formula R¹NH—[(CR³R⁴)_m—NH]_n—R²(II), where n is an integer from 0 to 20 and m is an integer from 2 to 4, the radicals R³and R⁴independently are C₁-C₃₀-hydrocarbyl radicals, preferably C₁-C₁₅-hydrocarbyl radicals, and the radicals R¹and R²independently of one another are C₁-C₃₀-hydrocarbyl radicals, preferably C₁-C₁₅-hydrocarbyl radicals or may together form a cycle. The bleaching performance boosters disclosed in DE-A 196 11 992 are an integral part of the present invention and are incorporated herein by reference.

The N-alkylammoniumacetonitrile salts coated according to the invention are, in particular, used with the bleaching performance boosters disclosed in the abovementioned application. In this case, particularly good results with regard to the bleach activator/bleaching performance booster combination are obtained. Here mention is of course inter alia to be made of the achieved bleaching action which is particularly marked and thus in principle desired. It has been found that this bleaching action, in the case of the combination of the noncoated N-alkylammoniumacetonitrile salts of the formula (I) described in the Application DE 199 13 996 with bleach activator can lead to undesired effects. In this connection, mention should be made to pinhole spotting. This term is understood as meaning punctiform damage to dyed textile fabrics which arises as a result of undesired, premature-partial hydrolysis of the salt (I), resulting in the local overconcentration of bleach activator/bleaching performance boosters and damage as a result of too severe local bleaching at the affected site. As a result of the coating according to the invention, such pinhole spotting is avoided.

The granular N-alkylammoniumacetonitriles coated according to the invention can be used as bleach activators for application in detergents, cleaners, dishwashing detergents, stain-removal salts, disinfectants, denture cleaners, fiber bleaching, for example cellulose bleaching, wood pulp bleaching or in cotton fiber bleaching, and also hair bleaching. Preferred areas of use are detergents and dishwashing detergents.

The bleach activators are used in the formulations intended in each case for these areas of application preferably in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 0.5 to 8% by weight and particularly preferably 0.8 to 5% by weight, based on the total formulation. The main fields of application are household and industrial textile detergents and household and industrial dishwashing formulations. The formulations in which the granular N-alkylammoniumacetonitriles coated according to the invention can be used are described below by way of example for the areas of application of textile detergents and machine dishwashing detergents.

As a result of the coating according to the invention, the substances of the formula (I) are easy and safe to handle, and virtually no formation of dust is observed. The substances are protected from undesired hydrolysis, which, for example, occurs readily in detergent formulations.

Household Textile Deterrent Composition

The detergent formulations in which the coated, granular N-alkylammoniumacetonitriles according to the invention can be used are pulverulent, granular, pasty, gelatinous or liquid, or they are solid detergent tablets. Depending on their intended use, the formulations are matched with regard to their composition to the type of textiles to be washed. They comprise conventional detergent ingredients which correspond to the prior art. Representative examples of such detergent and cleaner ingredients are described below.

The total concentration of surfactants in the finished detergent formulation can be from 1 to 99% by weight, preferably from 5 to 80% by weight. The surfactants used may be anionic, nonionic, amphoteric or cationic. It is also possible to use mixtures of said surfactants. Preferred detergent formulations comprise anionic and/or nonionic surfactants and mixtures thereof with further surfactants.

Suitable anionic surfactants are sulfates, sulfonates, carboxylates, phosphates and mixtures thereof. Suitable cations in this connection are alkali metals, for example sodium or potassium or alkaline earth metals, such as calcium or magnesium, and also ammonium, substituted ammonium compounds, including mono-, di- or triethanolammonium cations and mixtures thereof. Amongst the anionic surfactants, preference is given to alkyl ester sulfonates, alkyl sulfates, alkyl ether sulfates, alkylbenzenesulfonates, secondary alkane-sulfonates and soaps. These are described below.

Alkyl ester sulfates are, inter alia, linear esters of C ₁₈-C₂₀-carboxylic acids (fatty acids) which are sulfonated using gaseous SO₃, as described, for example, in “The Journal of the American Oil Chemists Society” 52 (1975), p. 323-329. Suitable starting materials are natural fats, such as tallow, coconut oil and palm oil, but also fats of a synthetic nature. Preferred alkyl ester sulfonates are compounds of the formula

in which R ¹is a C₈-C₂₀-hydrocarbon radical, preferably alkyl, and R is a C₁-C₆-hydrocarbon radical, preferably alkyl. M is a cation which forms a water-soluble salt with the alkyl ester sulfonate. Suitable cations are sodium, potassium, lithium or ammonium cations, for example monoethanolamine, diethanolamine and triethanolamine. Preferably, R¹is C₁₀-C₁₆-alkyl and R is methyl, ethyl or isopropyl. Methyl ester sulfonates in which R¹is C₁₀-C₁₆-alkyl are most preferred.

Alkyl sulfates are water-soluble salts or acids of the formula ROSO ₃M, in which R is a C₁₀-C₂₄-hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical with C₁₀-C₂₀-alkyl component, particularly preferably a C₁₂-C₁₈-alkyl or hydroxyalkyl radical. M is hydrogen or a suitable cation, e.g. an alkali metal cation, preferably sodium, potassium, lithium or an ammonium or substituted ammonium cation, preferably a methyl, dimethyl and trimethylammonium cation or a quaternary ammonium cation, such as the tetramethylammonium and dimethylpiperidinium cations, and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof. Alkyl chains with C₁₂-C₁₆are preferred for low washing temperatures (e.g. below about 50° C.) and alkyl chains with C₆-C₁₈are preferred for higher washing temperatures (e.g. above about 50° C.).

Alkyl ether sulfates are water-soluble salts or acids of the formula RO(A) _mSO₃M, in which R is an unsubstituted C₁₀-C₂₄-alkyl or hydroxyalkyl radical, preferably a C₁₂-C₂₀-alkyl or hydroxyalkyl radical, particularly preferably a C₁₂-C₁₈-alkyl or hydroxyalkyl radical. A is an ethoxy or propoxy unit, m is a number greater than 0, preferably between about 0.5 and about 6, particularly preferably between about 0.5 and about 3 and M is a hydrogen atom or a cation, such as sodium, potassium, lithium, calcium, magnesium, ammonium or a substituted ammonium cation. Examples of substituted ammonium cations include methyl-, dimethyl-, trimethylammonium and quaternary ammonium cations, such as tetramethylammonium and dimethylpiperidinium cations, and also those which are derived from alkylamines such as ethylamine, diethylamine, triethylamine or mixtures thereof. Examples which may be mentioned are C₁₂-C₁₈-fatty alcohol ether sulfates, the content of ethylene oxide units being 1, 2, 2.5, 3 or 4 mol per mole of the fatty alcohol ether sulfate and M being sodium or potassium.

In secondary alkanesulfonates, the alkyl group can either be saturated or unsaturated, branched or linear and may be substituted by an hydroxyl group. The sulfo group can be at any position in the carbon chain, the primary methyl groups at the start of the chain and at the end of the chain having no sulfonate groups. The preferred secondary alkanesulfonates contain linear alkyl chains having about 9 to 25 carbon atoms, preferably about 10 to about 20 carbon atoms and particularly preferably about 13 to 17 carbon atoms. The cation is, for example, sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof. Sodium is the preferred cation.

Further suitable anionic surfactants are alkenyl- or alkylbenzenesulfonates. The alkenyl or alkyl group can be branched or linear and may be substituted by a hydroxyl group. The preferred alkylbenzenesulfonates contain linear alkyl chains having about 9 to 25 carbon atoms, preferably from about 10 to about 13 carbon atoms, and the cation is sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof. For mild surfactant systems magnesium is the preferred cation, while sodium is preferred for standard washing applications. The same applies to alkenylbenzenesulfonates.

The term anionic surfactant also includes olefinsulfonates which are obtained by sulfonation of C ₁₂-C₂₄-, preferably C₁₄-C₁₆-α-olefins with sulfur trioxide and subsequent neutralization. Owing to the preparation process, these olefinsulfonates may contain relatively small amounts of hydroxyalkanesulfonates and alkanedisulfonates. Specific mixtures of α-olefin-sulfonates are described in U.S. Pat. No. 3,332,880.

Further preferred anionic surfactants are carboxylates, e.g. fatty acid soaps and comparable surfactants. The soaps may be saturated or unsaturated and can contain various substituents, such as hydroxyl groups or a-sulfonate groups. Preference is given to linear saturated or unsaturated hydrocarbon radicals as the hydrophobic moiety having about 6 to about 30, preferably about 10 to about 18 carbon atoms.

Other suitable anionic surfactants are: salts of acrylaminocarboxylic acids; the acyl sarcosinates formed by reacting fatty acid chlorides with sodium sarcosinate in an alkaline medium; fatty acid/protein condensation products obtained by reacting fatty acid chlorides with oligopeptides; salts of alkylsulfamidocarboxylic acids; salts of alkyl- and alkylaryl ether carboxylic acids; C ₈-C₂₄-olefinsulfonates; sulfonated polycarboxylic acids prepared by sulfonation of the pyrolysis products of alkaline earth metal citrates, as described, for example, in GB-1,082,179; alkyl glycerol sulfates, oleyl glycerol sulfates; alkylphenol ether sulfates; primary paraffinsulfonates; alkyl phosphates; alkyl ether phosphates; isethionates, such as acyl isethionates; N-acyltaurides; alkyl succinates; sulfosuccinates; monoesters of sulfosuccinates (particularly saturated and unsaturated C₁₂-C₁₈-monesters) and diesters of sulfosuccinates (particularly saturated and unsaturated C₁₂-C₁₈-diesters); acyl sarcosinates; sulfates of alkylpolysaccharides, such as, for example, sulfates of alkylpolyglycosides, branched primary alkylsulfates and alkylpolyethoxycarboxylates, such as those of the formula RO(CH₂CH₂)_kCH₂COO⁻M⁺, in which R is C₈- to C₂₂-alkyl, k is a number from 0 to 10 and M is a cation; resin acids or hydrogenated resin acids, such as, for example, rosin or hydrogenated rosin or tall oil resins and tall oil resin acids. Further examples are described in “Surface Active Agents and Detergents” (Vol. I and II, Schwartz, Perry and Berch).

Examples of suitable nonionic surfactants are:

polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols.

These compounds include the condensation products of alkylphenols having a C ₆-C₂₀-alkyl group, which may be either linear or branched, with alkene oxides. Preference is given to compounds containing about 5 to 25 mol of alkylene oxides per mole of alkylphenol.

Condensation products of aliphatic alcohols with about 1 to about 25 mol of ethylene oxide.

The alkyl chain of the aliphatic alcohols may be linear or branched, primary or secondary and generally contains about 8 to about 22 carbon atoms. Particular preference is given to the condensation products of C ₁₀-C₂₀-alcohols with about 2 to about 18 mol of ethylene oxide per mol of alcohol. The alkylene chain can be saturated or unsaturated. The alcohol ethoxylate can have a narrow homolog distribution (“Narrow Range Ethoxylates”) or a broad homolog distribution of the ethylene oxide (“Broad Range Ethoxylates”). Examples of commercially available nonionic surfactants of this type are, for example, the Lutensol® products from BASF Aktiengesellschaft.

Condensation products of ethylene oxide with a hydrophobic base, formed by condensation of propylene oxide with propylene glycol.

The hydrophobic moiety of these compounds preferably has a molecular weight between about 1 500 and about 1 800. The addition of ethylene oxide to this hydrophobic moiety leads to an improvement in the solubility in water. The product is liquid up to a polyoxyethylene content of about 50% of the total weight of the condensation product, which corresponds to a condensation with up to about 40 mol of ethylene oxide. Commercially available examples of this product class are, for example, the Pluronic® products from BASF Aktiengesellschaft.

Condensation products of ethylene oxide with a reaction product of propylene oxide and ethylenediamine.

The hydrophobic unit of these compounds consists of the reaction product of ethylenediamine with excess propylene oxide and generally has a molecular weight of from about 2 500 to 3 000. Ethylene oxide is added onto this hydrophobic unit until the product has a content of from about 40 to about 80% by weight of polyoxyethylene and a molecular weight of from about 5 000 to 11 000. Commercially available examples of this compound class are the Tetronic® products from BASF Corp.

Semipolar nonionic surfactants

This category of nonionic compounds includes water-soluble amine oxides, water-soluble phosphine oxides and water-soluble sulfoxides, each having an alkyl radical of from about 10 to about 18 carbon atoms. Semipolar nonionic surfactants are also amine oxides of the formula

where R is an alkyl, hydroxyalkyl or alkylphenol group with a chain length of from about 8 to about 22 carbon atoms. R ²is an alkylene or hydroxyalkylene group having about 2 to 3 carbon atoms or mixtures thereof, each radical R¹is an alkyl or hydroxyalkyl group having about 1 to about 3 carbon atoms or a polyethylene oxide group having about 1 to about 3 ethylene oxide units, and x is a number from 0 to about 10. The R¹groups can be joined together via an oxygen or nitrogen atom, thus forming a ring. Amine oxides of this type are, in particular, C₁₀-C₁₈-alkyldimethylamine oxides and C₈-C₁₂-alkoxyethyldihydroxyethylamine oxides.

Fatty acid amides

Fatty acid amides have the formula

in which R is an alkyl group having about 7 to about 21, preferably about 9 to about 17, carbon atoms, and R ¹, independently of the others, is hydrogen, C₁-C₄-alkyl, C₁-C₄-hydroxyalkyl or (C₂H₄O)_xH, where x varies from about 1 to about 3. Preference is given to C₈-C₂₀-amides, -monoethanolamides, -diethanolamides and -isopropanolamides.

Further suitable nonionic surfactants are alkyl- and alkenyloligoglycosides, and also fatty acid polyglycol esters or fatty amine polyglycol esters each having 8 to 20, preferably 12 to 18, carbon atoms in the fatty alkyl radical, alkoxylated triglycamides, mixed ethers or mixed formals, alkyloligoglycosides, alkenyloligoglycosides, fatty acid N-alkylglucamides, phosphine oxides, dialkyl sulfoxides and protein hydrolysates.

Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates or amphoteric imidazolinium compounds of the formula

in which R ¹is C₈-C₂₂-alkyl or -alkenyl, R²is hydrogen or CH₂CO₂M, R³is CH₂CH₂OH or CH₂CH₂OCH₂CH₂CO₂M, R⁴is hydrogen, CH₂CH₂OH or CH₂CH₂COOM, Z is CO₂M or CH₂CO₂M, n is 2 or 3, preferably 2, M is hydrogen or a cation, such as an alkali metal, alkaline earth metal, ammonium or alkanolammonium cation.

Preferred amphoteric surfactants of this formula are monocarboxylates and dicarboxylates. Examples thereof are cocoamphocarboxypropionate, cocoamidocarboxypropionic acid, cocoamphocarboxyglycinate (also referred to as cocoamphodiacetate) and cocoampho acetate.

Further preferred amphoteric surfactants are alkyldimethylbetaines and alkyldipolyethoxybetaines with an alkyl radical having about 8 to about 22 carbon atoms which may be linear or branched, preferably having 8 to 18 carbon atoms and particularly preferably having 12 to 18 carbon atoms.

Suitable cationic surfactants are substituted or unsubstituted straight-chain or branched quaternary ammonium salts of the type R ¹N(CH₃)₃ ⁺X⁻, R¹R²N(CH₃)₂ ⁺X⁻, R¹R²R³N(CH₃)⁺X⁻ or R¹R²R³R⁴N⁺X⁻. The radicals R¹, R², R³and R⁴are, independently of one another, preferably unsubstituted alkyl having a chain length of from 8 to 24 carbon atoms, in particular from 10 to 18 carbon atoms, hydroxyalkyl having 1 to 4 carbon atoms, phenyl, C₂-C₁₈-alkenyl, C₇-C₂₄-aralkyl, (C₂H₄O)_xH, where x is an integer from 1 to 3, alkyl radicals containing one or more ester groups, or cyclic quaternary ammonium salts. X is a suitable anion known to the person skilled in the art.

Further detergent and cleaner ingredients which may be present in the present invention include inorganic and/or organic builders in order to reduce the degree of hardness of the water.

These builders may be present in proportions by weight of about 5% to about 80% in the detergent and cleaner compositions. Inorganic builders include, for example, alkali metal, ammonium and alkanolammonium salts of polyphosphates, such as, for example, tripoly-phosphates, pyrophosphates and glass-like polymeric metaphosphates, phosphonates, silicates, carbonates including bicarbonates and sesquicarbonates, sulfates and aluminosilicates.

Examples of silicate builders are the alkali metal silicates, in particular those with an SiO ₂:Na₂O ratio between 1.6:1 and 3.2:1, and also phyllosilicates, for example the sodium phyllosilicates described in U.S. Pat. No. 4,664,839, available from Clariant GmbH under the tradename SKS®. SKS-6® is a particularly preferred phyllosilicate builder.

Aluminosilicate builders are particularly preferred for the present invention. These are, in particular, zeolites of the formula Na _z[(AlO₂)_z(SiO₂)_y—xH₂O, in which z and y are integers of at least 6, the ratio of z to y is from about 1.0 to 0.5, and x is an integer from 15 to 264.

Suitable ion exchangers based on aluminosilicate are available commercially. These aluminosilicates may be of crystalline or amorphous structure and may be naturally occurring or else prepared synthetically. Processes for the preparation of ion exchangers based on aluminosilicate are, for example, described in U.S. Pat. Nos. 3,985,669 and 4,605,509. Preferred ion exchangers based on synthetic crystalline aluminosilicates are available under the name zeolite A, zeolite P (B) (including those disclosed in EP-A-0 384 070) and zeolite X. Preference is given to aluminosilicates having a particle diameter between 0.1 and 10 μm.

Suitable organic builders include polycarboxyl compounds, such as, for example, ether polycarboxylates and oxydisuccinates, as described, for example, in U.S. Pat. Nos. 3,128,287 and 3,635,830. Also suitable are the TMS/TDS builders known from U.S. Pat. No. 4,663,071.

Other suitable builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, the alkali metal, ammonium and substituted ammonium salts of polyacetic acids, such as, for example, ethylenediaminetetraacetic acid and nitriloacetic acid, and polycarboxylic acid, such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate-based builders, e.g. citric acid and its soluble salts, in particular the sodium salt, are preferred polycarboxylic acid builders, which may also be used in granulated formulations, in particular together with zeolites and/or phyllosilicates.

Further suitable builders are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds which are disclosed in U.S. Pat. No. 4,566,984.

If builders based on phosphorus can be used and particularly if the intention is to formulate bar soaps for washing by hand, various alkali metal phosphates, such as, for example, sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate may be used. It is likewise possible to use phosphonate builders, such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates as disclosed, for example, in U.S. Pat. Nos. 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137.

In general, the detergent ingredients used with the salts of the formula (I) coated according to the invention are chosen from components typical for cleaners, such as surface-active substances and builders. Where appropriate, the cleaner ingredients may comprise one or more cleaning auxiliaries or other materials which enhance the cleaning action, serve for the treatment or care of the article being cleaned or change the use properties of the cleaning composition. Suitable cleaning auxiliaries in cleaning compositions include, for example, those substances specified in U.S. Pat. No. 3,936,537. The cleaning auxiliaries which may be used in the cleaning compositions of the present invention include, for example, enzymes, in particular proteases, lipases and cellulases, foam boosters, foam suppressors, discoloration and/or corrosion inhibitors, suspending agents, dyes, fillers, optical brighteners, disinfectants, alkalis, hydrotropic compounds, antioxidants, enzyme stabilizers, perfumes, solvents, solubility promoters, redeposition inhibitors, dispersants, color transfer inhibitors, e.g. polyamine N-oxides, such as, for example, poly(4-vinylpyridine N-oxide), polyvinylpyrrolidone, poly-N-vinyl-N-methylacetamide and copolymers of N-vinylimidazole and N-vinylpyrrolidone, processing auxiliaries, softeners and antistatic auxiliaries.

Bleaches typically used in combination with the coated, granular N-alkylammoniumacetonitriles according to the invention are described above.

As well as comprising the coated, granular N-alkylammoniumacetonitriles according to the invention, the detergent compositions may comprise one or more conventional enzymes, such as proteases, amylases, lipases and cellulases. A particularly preferred enzyme is cellulase. The cellulase used here can be obtained from bacteria or fungi and should have an optimum pH range between 5 and 9.5. Suitable celluloses are disclosed in U.S. Pat. No. 4,435,307. This is a cellulase produced from a strain of Humicola insulins, in particular from the strain Humicola DSM 1800 or another cellulase-212-producing fungus belonging to the genus Aeromonas, and also cellulase extracted from the hepatopancreas of certain marine mollusks. Suitable cellulases are also disclosed in GB-A-2,075,028, GB-A-2,085,275 and DE-A-2,247,832.

Suitable cellulases are described in WO-91/17243. The cleaning compositions according to the invention comprise enzymes in amounts up to about 50 mg, preferably from about 0.01 mg to about 10 mg, per gram of the cleaning composition. Based on the weight of the cleaning compositions, the proportion of the enzymes is at least 0.001% by weight, preferably from about 0.001% by weight to about 5% by weight, in particular from about 0.001% by weight to about 1% by weight, specifically from about 0.01% by weight to about 1% by weight.

Machine Dishwashing and Detergent Composition

Builders: It is possible to use water-soluble and water-insoluble builders whose main aim consists in binding calcium and magnesium. Customary builders, which may be present in amounts between 10 and 90% by weight, based on the total preparation, are listed below.

Phosphates, such as, for example, alkali metal phosphates and polymeric alkali metal phosphates, which may be in the form of their alkali, neutral or acidic sodium or potassium salts. Examples thereof are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogenphosphate, pentasodium tripolyphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate having degrees of oligomerization of from 5 to 1 000, in particular from 5 to 50, and the corresponding potassium salts and mixtures of sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts. These phosphates are preferably used in the range from 25% by weight to 65% by weight, based on the overall formulation and calculated as anhydrous active substance.

Low molecular weight carboxylic acids and their salts, such as, for example, alkali metal citrates (such as e.g. anhydrous trisodium citrate or trisodium citrate dihydrate), alkali metal succinates, alkali metal malonates, fatty acid sulfonates, oxydisuccinates, alkyl or alkenyl disuccinates, gluconic acids, oxadiacetates, carboxymethyloxysuccinates, tartrate monosuccinate, tartrate disuccinate, tartrate monoacetate, tartrate diacetate, α-hydroxypropionic acid, oxidized starches, oxidized polysaccharides; homo- and copolymeric polycarboxylic acids and their salts, such as e.g. polyacrylic acid, polymethacrylic acid, maleic acid/acrylic acid copolymer, maleic acid/acrylic acid/vinyl acetate copolymer; graft polymers of monoethylenically unsaturated mono- and/or dicarboxylic acids on monosaccharides, oligosaccharides, polysaccharides or polyaspartic acid; aminopolycarboxylates and polyaspartic acid; carbonates, such as, for example, sodium carbonate and sodium bicarbonate.

Complexing agents and phosphonates and salts thereof, such as e.g. nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, methylglycinediacetic acid, 2-phosphono-1,2,4-butanetricarboxylic acid, aminotri(methylenephosphonic acid), 1-hydroxyethylene(1,1-diphosphonic acid), ethylenediaminetetramethylenephosphonic acid, hexamethylene-diaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid.

Silicates, such as, for example, sodium disilicate and sodium metasilicate. Water-insoluble builders include the zeolites and crystalline phyllosilicates, the latter corresponding in particular to the formula NaMSi _xO_2x+1*yH₂O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably 1.9 to 4, and y is a number from 0 to 33. Known examples thereof are, in particular, α-Na₂Si₂O₅, β-Na₂Si₂O₅, δ-Na₂Si₂O₅. They also include mixtures of the abovementioned builder substances. Preference is given to using trisodium citrate and/or pentasodium tripolyphosphate and/or sodium carbonate and/or sodium bicarbonate and/or gluconates and/or silicatic builders from the class of disilicates and/or metasilicates.

Alkali carriers: Further constituents which may be present are alkali carriers. Alkali carriers used are alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, alkali metal silicates, alkali metal metasilicates and mixtures of the above substances, preference being given to using the alkali metal carbonates, in particular sodium carbonate, sodium hydrogencarbonate or sodium sesquicarbonate. Preferred combinations of builder and alkali carrier are mixtures of tripolyphosphate and sodium carbonate or tripolyphosphsate, sodium carbonate and sodium disilicate.

Surfactants: Preference is given to using weakly or low-foaming nonionic surfactants in amounts of from 0.1 to 20% by weight (preferably 0.1-10% by weight, 0.25-4% by weight). These are, for example, surfactants from the group of fatty alcohol ethoxylates, as are commercially available, for example, under the product names Plurafac® (BASF Aktiengesellschaft) or Dehypon® (Cognis). It is also possible to use di- and multiblock copolymers constructed from ethylene oxide and propylene oxide, as are commercially available, for example, under the name Pluronic® (BASF Aktiengesellschaft) or Tetronic® (BASF Corporation). It is also possible to use reaction products of sorbitan esters with ethylene oxide and/or propylene oxide. Amine oxides or alkylglycosides are likewise suitable. An overview of suitable nonionic surfactants is given, for example, in EP-A 0851 023 and DE-A 198 19 187.

The formulation can also comprise anionic or zwitterionic surfactants, preferably in a mixture with nonionic surfactants. Suitable anionic and zwitterionic surfactants are likewise given in the specifications EP-A 0851 023 and DE-A 198 19 187.

Bleaches typically used in combination with the salts of the formula (I) used according to the invention are described above.

Corrosion inhibitors: In particular, it is possible to use silver protectants from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and the transition metal salts or complexes. Particular preference is given to using benzotriazole and/or alkylaminotriazole. Moreover, agents containing active chloride are frequently found in cleaning formulations; these are able to significantly reduce corrosion on silver surfaces. In chlorine-free cleaners, preference is given to using oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trifunctional phenols, e.g. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol, and derivatives of these classes of compound. Salt- and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are also frequently used. Preference is given here to the transition metal salts chosen from the group of manganese and cobalt salts and complexes thereof, particular preference being given to cobalt (ammine) complexes, cobalt (acetato) complexes, cobalt (carbonyl) complexes, chlorides of cobalt and of manganese and manganese sulfate. It is also possible to use zinc compounds or bismuth compounds for preventing corrosion on the ware.

Enzymes: Between 0 and 5% by weight of enzymes, based on the overall preparation, may be added to the cleaner to increase the power of the cleaners or, under milder conditions, to ensure cleaning power of equal quality. The most frequently used enzymes include lipases, amylases, cellulases and proteases. It is also possible to use esterases, pectinases, lactases and peroxidases. Preferred proteases are e.g. BLAP® 140 from Biozym, Optimase® M-440 and Opticlean® M-250 from Solvay Enzymes; Maxacal® CX and Maxapem® or Esperase® from Gist Brocades or Savinase® from Novo or Purafect® OxP from Genencor. Particularly suitable cellulases and lipases are Celluzym® 0.7T and Lipolase® 30 T from Novo Nordisk. The amylases which are particularly used are Duramyl® and Termamyl® 60 T, and Termamyl® 90 T from Novo, Amylase-LT® from Solvay Enzymes, Maxamyl® P5000 from Gist Brocades or Purafect® OxAm from Genencor. It is also possible to use other enzymes.

Further additives: Paraffin oils and silicone oils may optionally be used as antifoams and for the protection of plastic and metal surfaces. Antifoams are generally added in amounts of from 0.001% to 5%.

The coated, granular N-alkylammoniumacetonitriles according to the invention can be used in cleaning formulations both for the household sector and also for the industrial sector. Industrial types of cleaner mostly comprise a builder system based on pentasodium triphosphate, and/or sodium citrate and/or complexing agents such as e.g. nitrilotriacetate. In contrast to household cleaners, they are frequently used with sodium hydroxide solution or potassium hydroxide solution as alkali carrier.

The coated, granular N-alkylammoniumacetonitriles according to the invention can be used either in liquid, gel, pulverulent, granular or tablet form. It is possible to incorporate the coated, granular N-alkylammoniumacetonitriles according to the invention, optionally with other formulation constituents, into particular compartments, such as e.g. microcapsules, gel capsules. Furthermore, the copolymers according to the invention can also be incorporated into specific compartments within dishwasher tablets which may be able to exhibit a different dissolution behavior to that of the other tablet compartments. These may either be distinct tablet layers, or distinct moldings incorporated into the tablet, stuck to the tablet or surrounded by the tablet.

The invention will now be illustrated in the examples below. The abbreviations have the meanings known to the person skilled in the art.

EXAMPLES

Example 1

Preparation of Granular N-Methylmorpholiniumacetonitrile Hydrogensulfate (MMA) [0117]
An 80 liter glass container was charged with 60 liters of a 65% strength by weight aqueous solution of N-methylmorpholiniumacetonitrile methylsulfate. The solution was heated to 110° C. and evaporated at a pressure of 600 mbar over a period of 3 hours. The melt, which had a content of N-methylmorpholiniumacetonitrile hydrogensulfate of about 80% by weight (the remainder consisted essentially of inorganic salts and water), was then applied, in a 160 liter Lödige mixer, to 16 kg of a commercially available silica, and the mixture was solidified. The solidified mixture was then screened to a particle size of from 350 to 1600 micrometers. The coarse material greater than 1 600 micrometers was ground and then screened again. This gave a granular granulate with a content of about 60% by weight of N-methylmorpholiniumacetonitrile hydrogensulfate. [0118]

Example 2

Preparation of Granular Trimethylammoniumacetonitrile Hydrogensulfate (TMAQ) [0119]
An 80 liter glass container was charged with 60 liters of a 48% strength by weight aqueous solution of trimethylammoniumacetonitrile methylsulfate. The solution was heated to 110° C. and evaporated at a pressure of 500 mbar over a period of 4 hours. The melt, which had a content of trimethylammoniumacetonitrile hydrogensulfate of about 80% by weight (the remainder consisted essentially of inorganic salts and water), was then applied, in a 160 liter Lödige mixer, to 12 kg of a commercially available silica, and the mixture was solidified. The solidified mixture was then screened to a particle size of from 350 to 1 600 micrometers. The coarse material greater than 1 600 micrometers was ground and then screened again. This gave a granular granulate with a content of about 60% by weight of N-methylmorpholiniumacetonitrile hydrogensulfate. [0120]

Example 3

Coating of Granular N-Methylmorpholiniumacetonitrile Hydrogensulfate with Polyethylene Glycol Mw 6000 (15% Loading) [0121]
2 kg of granular N-methylmorpholiniumacetonitrile hydrogensulfate were introduced into a bench spray fluidized bed and fluidized using air at room temperature. A heated receiving container was charged with 300 g of solid polyethylene glycol Mw 6 000 and melted at a temperature of 80° C. The melt was sprayed into the fluidized bed via a heated nozzle over a period of 30 minutes and thus coated the fluidized methylmorpholiniumacetonitrile hydrogensulfate granules. [0122]

Example 4

Coating of Granular Trimethylammoniumacetonitrile Hydrogensulfate with an Aqueous Dispersion of a Copolymer of Ethyl Acrylate and Methacrylic Acid (Weight Ratio 1:1, Mw 250 000) (10% Loading) [0123]
2 kg of trimethylammoniumacetonitrile hydrogensulfate were introduced into a bench spray fluidized bed and fluidized using air at 65° C. 1 kg of an aqueous dispersion of a copolymer of ethyl acrylate and methacrylic acid (solids content 20% by mass) were introduced into a stirred receiving vessel. After the fluidized bed had reached a temperature of 50° C., the dispersion was sprayed in over a period of 2.5 hours. After the spraying, the coated particles were then dried at an air temperature of 40° C. for a period of 30 minutes. [0124]

Example 5

Coating of Granular Trimethylammoniumacetonitrile Hydrogensulfate with Stearic Acid (10% Loading) [0125]

2 kg trimethylammoniumacetonitrile hydrogensulfate were introduced into a bench spray fluidized bed and fluidized using air at room temperature. 200 g of solid stearic acid were introduced into a heated receiving container and melted with stirring at a temperature of 85° C. The melt was sprayed into the fluidized bed via a heated nozzle over a period of 45 minutes.

The coating of Examples 6-16 was carried out analogously to Examples 3-5:

	Bleach
Example #	activator	Carrier material	Coating material	Loading

6	MMA	Precipitated silica	Stearic acid	35%
7	MMA	Precipitated silica	C₁₆-C₁₈fatty alcohol + 80	10%
			ethylene glycol units
8	MMA	Precipitated silica	Poly(vinylpyrrolidone-co-	12%
			vinyl acetate 60:40), Mw
			60 000
9	MMA	Precipitated silica	Polyoctadecylvinyl ether, Mw	8%
			30 000
10	MMA	Precipitated silica	Montanic acid wax, m.p. 80° C.	6%
11	TMAQ	Precipitated silica	Pluronic ®PE 6800	15%
12	TMAQ	Precipitated silica	C₁₆-C₁₈fatty alcohol + 80	6%
			ethylene glycol units
13	TMAQ	Precipitated silica	Poly(vinylpyrrolidone-co-	8%
			vinyl acetate 60:40), Mw
			60 000
14	TMAQ	Precipitated silica	Poloctadecylvinyl ether, Mw	10%
			30 000
15	TMAQ	Precipitated silica	Montanic acid wax, m.p. 80° C.	12%
16	TMAQ	Precipitated silica	Pluronic ® PE 6800	15%

Example 17

Testing the Spotting Behavior [0127]
Method [0128]
6 colored fabrics (reactive red 21 on cotton) measuring 10 cm×10 cm are placed into a shallow plastic tub measuring 30 cm×50 cm and covered with a metallic mesh measuring 25 cm×45 cm (hole diameter 5 mm). 250 ml of mains water (temperature 21° C., water hardness 3.5 mmol/l) are added to the tub such that the fabrics are completely covered. 5 g of the detergent formulation are applied uniformly to each fabric. The damp detergent is allowed to act on the fabric for 10 minutes at 21° C. The fabric is then rinsed with mains water and dried. [0129]

The spotting damage is evaluated visually according to the following scale:



Grade	Finding

1	Severe color damage over a large area, with visibly white areas
2	Relatively large areas with color changes
3	Minor punctiform color change
4	Slight, very minor punctiform color changes
5	No color change noted to the starting fabric

Test Formulation [0131]

The detergent formulation used for the spotting behavior test has the following composition:



Constituent	Proportion by mass [%]

Na C_12-14-alkylbenzenesulfonate	7.9
C_13-15-oxo alcohol-7EO	6.4
Soap	1.5
Zeolite P	31.0
Soda	23.0
Sodium percarbonate	14.6
Bleach activator*	4.1
Sodium metasilicate	5.4
Sodium citrate	1.7
Ethylenediaminetetramethylenephosphonate	0.2
Sokalan ® CP 5 granulate	1.6
Sokalan ® HP 53 granulate	0.1
Sodium sulfate	2.5

Test Results



Bleach activator	Spotting behavior

N-Methylmorpholiniumacetonitrile	2
hydrogensulfate, uncoated
Trimethylanimoniumacetonitrile hydrogensulfate,	2
uncoated
Example 3	4
Example 4	5
Example 5	5
Example 5	5
Example 6	4
Example 7	4
Example 8	4
Example 9	3
Example 10	4
Example 11	3
Example 12	3
Example 13	5
Example 14	5
Example 15	5
Example 16	4

Example 18

Stability in an Alkaline Cleaning Formulation [0134]
Method [0135]
10 g of the cleaning formulation below were stored open in a climatic chamber at 25° C. and 70% relative atmospheric humidity for 3 weeks. The nonhydrolyzed bleach activator was then determined analytically using HPLC. From this, the percentage of unchanged bleach activator, based on the starting content of activator taking into consideration the proportion of coating material, was calculated. [0136]

Cleaning Formulation



	Ingredients	Proportion by mass [%]

	Pentasodium triphosphate	48
	Polyacrylic acid Mw 8 000	1
	Sodium carbonate	22
	Sodium hydrogencarbonate	2
	Sodium disilicate	5.3
	Borax (disodium tetraborate)	2
	Sodium perborate monohydrate	10
	Bleach activator*	2
	Protease + amylase 1:1	1
	Plurafac ® LF 403	1.5
	Polyethylene glycol	4
	Perfume	0.2
	Dye	1

Test Results



		Proportion of unchanged
	Bleach activator	bleach activator [%]

	N-Methylmorpholiniumacetonitrile	45
	hydrogensulfate, uncoated
	Trimethylammoniumacetonitrile	29
	hydrogensulfate,
	uncoated
	Example 3	62
	Example 4	78
	Example 5	93
	Example 7	85
	Example 8	82
	Example 9	88
	Example 10	77
	Example 11	91
	Example 12	72
	Example 13	75
	Example 14	94
	Example 15	96
	Example 16	89

Example 19 (Comparative Example)

Bleaching Behavior [0139]
The procedure was carried out as a standard washing test in a Launder-o-Meter. The test fabric was a fabric of the type EMPA 114 which had been treated with red wine for the staining, or fabric of the type EMPA 167 (origin in each case: EMPA Testgewebe, St. Gallen, Switzerland), which had been treated with tea for the staining. When the experiment is complete, the reflectance (expressed in [%]) is measured using an Elrepho measuring device from Zeiss. [0140]

The laundry detergent has the following composition:



	Na C12-C14-alkylbenzenesulfonate	0.8%
	Na C12-C14-alkyl sulfate	12.0%
	Nonionic surfactants (C13-15-oxo alcohol-7 EO)	4.7%
	Soap	0.4%
	Zeolite A	15.0%
	Phyllosilicate	14.0%
	Mg silicate	0.8%
	Na hydrogencarbonate	9.0%
	Na citrate	5.0%
	Na polycarboxylate (Sokalan ® CP5, BASF)	5.0%
	CMC	0.6%
	Phosphonate	0.8%
	NaSO₄	3.2%
	Na percarbonate	18.0%
	Activator (optional)	5.0%
	Bleach booster (optional)	1.0%
	Remainder water

The results are given in the table below: [0142]

Bleaching Performance



	Bleaching		Reflectance, red
Activator	performance booster	Reflectance, tea	wine

—		31%	47%
MMA	—	51%	58%
MMA	HMI	50%	58%
MMA coated	—	45%	55%
MMA coated	HMI	48%	57%

Example 20 (Comparative Example)

The procedure was as for example 17, the fabric was EMPA 132 which had been stained with Direct Black 122. The color loss was measured using an Elrepho measuring device from Zeiss, the color loss [%] was calculated as follows: [0144]
(1-color intensity after testing/color intensity before testing)*100
Spotting effect: The evaluation was carried out as in example 17. [0145]
The results are given in the table below. [0146]

Color Damage



	Bleaching performance
Activator	booster	Color loss	Spotting

—	0%	5
MMA	—	18%	3
MMA	HMI	51%	1
MMA coated	—	2%	5
MMA coated	HMI	8%	5

Claims

We claim:

1. A granular, coated N-alkylammoniumacetonitrile salt of the formula (I)

R²R³NR¹—CR⁴R⁵—CN⁺Y⁻ (I)

in which

2. A granular, coated N-alkylammoniumacetonitrile salt as claimed in claim 1, wherein the coating materials are chosen from the group consisting of fatty alcohols, fatty alcohol/ammonium stearate mixtures, ethoxylated fatty alcohols, in particular C₈-C₃₁-fatty alcohol polyalkoxylates having 1 to 150 moles of ethylene oxide, ethoxylated oxo alcohols, fatty acids, in particular lauric acid, myristic acid, stearic acid and the Na, K, Ca and ammonium salts of these acids, fatty acid esters, waxes, in particular paraffin waxes, montan ester waxes, montan acid waxes, polyethylene waxes, oxidized polyethylene waxes, ethylene/acrylic acid copolymer waxes, ethylene/vinyl acetate copolymer waxes, polyalkyl vinyl ether waxes, dispersions as suitable polymers, in particular of polyalkyl acrylate, polystyrene, alkyl acrylate/(meth)acrylic acid copolymers, maleic acid/olefin copolymers, vinyl chloride/ethylene copolymers and vinyl chloride/ethylene/methacrylate copolymers.

3. A granular, coated N-alkylammoniumacetonitrile salt as claimed in claim 1, wherein the inorganic coating material is chosen from the group consisting of magnesium sulfate, sodium hexaphosphate, dihydrogen phosphate, pyrophosphate, phosphonic acids, sodium metaborate, sodium metasilicate, waterglass, sodium polyphosphate, sodium sulfate, sodium carbonate, sodium silicate, sodium bicarbonate, borax, magnesium sulfate and boric acid.

4. A granular, coated N-alkylammoniumacetonitrile salt as claimed in claim 1, wherein the organic, hydrophilic coating material is chosen from the group consisting of polyethylene glycols having a molecular weight of from 1 000 to 50 000 and block copolymers and random copolymers of ethylene glycol and propylene glycol.

5. A granular, coated N-alkylammoniumacetonitrile salt as claimed in any of claims 1 to 4, wherein the coating material is chosen from the group consisting of polyethylene glycols having a molecular weight ≧1 500, long-chain fatty acids, fatty alcohol ethoxylates and block copolymers of ethylene oxide and propylene oxide, in particular from the group consisting of polyethylene glycols having a molecular weight of about 6 000, fatty alcohol ethoxylates of C₁₆-C₁₈-fatty alcohols, ethylene oxide/propylene oxide block copolymers having an ethylene oxide content of about 80% and a molecular weight of about 8 000, and stearic acid.

6. A granular, coated N-alkylammoniumacetonitrile salt as claimed in any of claims 1 to 5, wherein R²and R³together with the nitrogen atom to which they are bonded form a six-membered ring which may optionally contain a further nitrogen atom or an oxygen atom, or R¹to R³are identical or different and are a C₁-C₄-alkyl radical, in particular N-methylmorpholiniumacetonitrile sulfate or hydrogensulfate or trimethylammoniumacetonitrile sulfate or hydrogensulfate.

7. A granular, coated N-alkylammoniumacetonitrile salt as claimed in any of claims 1 to 6, which is used in combination with other bleach activators, preferably polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), glucose pentaacetate (GPA), xylose tetraacetate (TAX), sodium 4-benzoyloxybenzenesulfonate (SBOBS), sodium trimethylhcxanoyloxybenzenesulfonate (STHOBS), tetraacetylglucoluril (TAGU), tetraacetylcyanic acid (TACA), di-N-acetyldimethylglyoxime (ADMG), 1-phenyl-3-acetylhydantoin (PAH), acylated phenolsulfonates, nonanoylbenzenesulfonates (NOBS), isononanoylbenzenesulfonates (isoNOBS), lauroylbenzenesulfonates (LOBS), carbonylbiscaprolactam and/or bis(2-propylimino)carbonate.

8. A granular, coated N-alkylammoniumacetonitrile salt as claimed in any of claims 1 to 7, which is used in combination with a bleaching performance booster, preferably a bleaching performance booster of a low molecular weight, oligomeric or polymeric compound containing secondary amine groups —NHR¹, in particular from the group consisting of secondary amines of the formula

R¹NH—[(CR³R⁴)_m—NH]N—R² (II)

where N is an integer from 0 to 20 and m is an integer from 2 to 4, the radicals R³and R⁴independently of one another are C₁-C₃₀-hydrocarbyl radicals, preferably C₁-C₁₅-hydrocarbyl radicals, and the radicals R¹and R²independently of one another are C₁-C₃₀-hydrocarbyl radicals, preferably C₁-C₁₅-hydrocarbyl radicals, which may together form a cyclic radical.

9. A granular, coated N-alkylammoniumacetonitrile salt as claimed in any of claims 1 to 8, which is used together with bleaches from the group consisting of alkali metal perborates and hydrates thereof, alkali metal percarbonates, in particular sodium perborate in the form of the mono- or tetrahydrate, sodium percarbonate and hydrates thereof, persulfates, hydrogen peroxide, oxygen bleaches, preferably organic peracids, in particular perbenzoic acid, peroxyalphanaphthoic acid, peroxylauric acid, peroxystearic acid, phthalimidoperoxycaproic acid, nonylimidoperoxysuccinic acid, nonylimidoperoxyadipic acid, 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelaic acid, diperoxoisophthalic acid, and 2-decyldiperoxybutane-1,4-dioic acid, cationic peroxy acids and sulfonylperoxy acids.

10. A process for the preparation of a granular, coated N-alkylammoniumacetonitrile salt as claimed in any of claims 1 to 9, which comprises applying a suitable coating material from the melt, solution or dispersion with removal of the solvent or dispersant by evaporation or in the form of a fine powder, preferably by applying the coating materials in a fluidized bed.

11. A bleach activator having at least one granular, coated N-alkylammoniumacetonitrile salt as claimed in any of claims 1 to 9.

12. A detergent, cleaner, dishwashing detergent, stain-removal salt, disinfectant, denture cleaner, fiber bleach, in particular cellulose bleach, wood pulp bleach or cotton fiber bleach, or a hair bleach, in particular a detergent or a dishwashing detergent, comprising at least one granular, coated N-alkylammoniumacetonitrile salt as claimed in any of claims 1 to 9.