DE10049237A1 - Coated, granular N-alkylammonium acetonitrile salts and their use as a bleach activator - Google Patents

Abstract

The invention relates to granular, coated N-alkylammonium acetonitrile salts of general formula (I) R<2>R<3>N R<1>-CR<4>R<5>-CN<+>Y<->, wherein R<1> means a C1- to C24-alkyl group which can be interrupted by non-adjacent oxygen atoms or can additionally carry hydroxyl groups, a C4- to C24-cycloalkyl group, a C7- to C24 alkaryl group or a grouping of formula -CR<4>R<5>-CN; R<2> and R<3> each have, independently of each other, the meaning of R<1> or together represent, in the nitrogen atom to which they are bonded, a saturated four to nine-membered ring with at least one C-atom and at least one other hetero atom from the following group: oxygen, sulphur and nitrogen; R<4> and R<5> each mean, independently of each other, hydrogen, a C1- to C24 alkyl group which can be interrupted by non-adjacent oxygen atoms or can additionally carry hydroxyl groups, a C4- to C24-cycloalkyl group or a C7- to C24-alkaryl group; and Y represents a sulphate or hydrogen sulphate anion in the appropriate stoichiometric quantity; which are coated with a material selected from the following group: organic, inorganic, hydrophilic and hydrophobic substances.

Description

The present invention relates to N-alkylammonium acetonitrile salts of the formula

R ² R ³ NR ¹ -CR ⁴ R ⁵ -CN ⁺ Y ^- (I)

in which R ¹ to R ⁶ and Y have the meaning given in the text, which are present in granular form and are coated. Because of their coating, the salts of the formula (I) are outstandingly suitable for use as bleach activators in detergents and dishwashing detergents.

Bleach activators have been used in modern washing and cleaning agents for some time used. They serve the purpose that are usually used as bleaching agents Activate connections in such a way that the decay of these connections completely and / or already occurs at low temperatures and thus the desired bleaching effect is achieved.

A large number of connection classes or connections exist Bleaching effect against a wide variety of substrates is known and therefore in the most diverse detergents and cleaning agents as well as generally in applications in Hygiene, personal care and industrial use as bleach. Generally, these are organic and inorganic peroxo compounds, frequently peroxo acids as well as perborates and percarbonates, which are in free form or in form the salts, preferably the alkali salts, are used. These peroxides disintegrate often not to the desired extent under the chosen conditions; for example a temperature is often chosen for washing, which does not lead to the disintegration of the Bleach is sufficient. In practice, it has therefore been shown to be necessary Connections when used in known applications with so-called  To provide bleach activators that cause the bleach used Connections disintegrate and the bleaching effect occurs.

In practice, the bleach activators are often coated with a layer provided, which makes them easier to dose and handle and often better Wash results result. In addition, they are less easily subject in coated form a hydrolysis, which is common in the usual washing and Detergent formulations due to their alkaline pH detergent substances easily occurs.

A known class of bleach activators are N-alkylammonium acetonitrile salts of the general formula

R ² R ³ NR ¹ -CR ⁴ R ⁵ -CN ⁺ Y ^- (I)

in the
R ^{1 is} a C ₁ to C ₂₄ alkyl group which can be interrupted by non-adjacent oxygen atoms or can additionally carry hydroxyl groups, a C ₄ to C ₂ cycloalkyl group, a C ₇ to C ₂₄ alkaryl group or a grouping of the formula - CR ⁴ R ⁵ -CN means
R ² and R ³ each independently of one another have the meaning of R ¹ or together represent a saturated four- to nine-membered ring with at least one carbon atom and at least one further hetero atom from the group consisting of oxygen, sulfur and nitrogen,
R ⁴ and R ^{5 are} each independently hydrogen, a C ₁ to C ₂₄ alkyl group which can be interrupted by non-adjacent oxygen atoms or can additionally carry hydroxyl groups, a C ₄ to C ₂₄ cycloalkyl group or a C ₇ to C ₂₄ -Alkaryl group means and
Y stands for a suitable anion.

This group of bleach activators is described in patent applications EP-A 303 520 (Kao Corporation, earliest priority date Aug. 14, 1987), WO 96/40661 (Clorox Company, Priority date 07.06.1995) and the applications EP-A 790 244 (Hoechst AG, Priority date February 15, 1996) and DE-A 197 40 669 (Clariant GmbH, filing date September 17, 1997). This last application mentioned above also describes wrapping (Coating) the compounds with a suitable substance.

While the nitriles disclosed in the applications cited in the previous section have excellent bleach activator properties, they still have certain disadvantages. For example, when using the commonly used counterions Cl ^- or CH ₃ OSO ₃ ^- in a non-granular, generally difficult to process and difficult to dose form, the production of these salts is also cumbersome, time-consuming and energy-intensive. There has been no shortage of attempts to convert these salts into a user-friendly form.

In the unpublished German application from BASF AG, the Case number 199 13 995.4 (filing date March 29, 1999) described a procedure that this Provides nitrile salts in granular, granular form. For this purpose, the respective nitrile, which is called Salt of methyl sulfate is present at a temperature of 80 to 250 ° C and a pressure evaporated from 10 mbar to 2 bar to a melt, which is then allowed to solidify. During the evaporation or afterwards, customary carrier materials and / or Auxiliary added and the nitrile thus obtained, the sulfate or hydrogen sulfate is present, converted to the crystalline state.

The process described above, disclosed in the German application with the file number 199 13 995.4, and the N-alkylammonium acetonitrile salts of Fomel (I), in which Y = HOSO ₃ ^- or SO ₄ ^2- , are obtainable as an integral part of present invention and incorporated therein by reference.

The salts available in this way, which in principle are excellent for use as Bleach activators in detergents and cleaning agents and other bleaching agents Applications are suitable, but need improvement with regard to handling. It As is the case with any chemical substance, it should be avoided that  unnecessarily large amounts are absorbed by the handling personnel. This is especially when granules that are not resistant to abrasion are present.

It is the object of the present invention to form the substances of the formula (I) in which R ¹ to R ^{6 have} the meaning given above and Y is a SO ₄ ^2- ion or an HSO ₃ ^- ion assemble, which enable a risk-free handling of the substances and at the same time ensure easy handling.

This object is achieved by a granular, coated N-alkylammonium acetonitrile salt of the general formula (I)

R ² R ³ NR ¹ -CR ⁴ R ⁵ -CN ⁺ Y ^- (I)

in the
R ^{1 is} a C ₁ to C ₂₄ alkyl group which can be interrupted by non-adjacent oxygen atoms or can additionally carry hydroxyl groups, a C ₄ to C ₂ cycloalkyl group, a C ₇ to C ₂₄ alkaryl group or a grouping of the formula - CR ⁴ R ⁵ -CN means
R ² and R ³ each independently of one another have the meaning of R ¹ or together represent a saturated four- to nine-membered ring with at least one carbon atom and at least one further hetero atom from the group consisting of oxygen, sulfur and nitrogen,
R ⁴ and R ^{5 are} each independently hydrogen, a C ₁ to C ₂₄ alkyl group which can be interrupted by non-adjacent oxygen atoms or can additionally carry hydroxyl groups, a C ₄ to C ₂₄ cycloalkyl group or a C ₇ to C ₂₄ -Alkaryl group means and
Y represents a sulfate or bisulfate anion of the corresponding stoichiometric amount,
wherein the salts of formula (I) are coated with a material which is selected from the group consisting of organic, inorganic, hydrophilic and hydrophobic substances.

The N-alkylammonium acetonitrile salts of the formula (I) coated according to the invention are by wrapping the after evaporation and transferring the salts into a granular shape corresponding to that in the application with the file number 199 13 995.4 disclosed methods obtained granules in a manner known per se manufactured. Both inorganic and organic, hydrophilic and 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 -C ₃₁ fatty alcohol polyalkoxylates with 1 to 150 moles of ethylene oxide, fatty acids, for example lauric acid, myristic acid, stearic acid and their Na, K, Ca and ammonium salts, fatty acid esters, waxes, for example paraffin waxes, montan ester wax, montanic acid wax, polyethylene wax, oxidized polyethylene wax, ethylene / acrylic acid copolymer wax, ethylene / vinyl acetate copolymer wax, poly alkyl 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 with a molecular weight of 1000 to 50,000 as well Block copolymers and statistical 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, water glass, 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 as a mixture with one or more other coating materials from the same group or come from another group.

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

Polyethylene glycols with a molecular weight ≧ 1500, long-chain are preferred Fatty acids, fatty alcohol ethoxylates (for example of the type Lutensol® from BASF AG) and Block copolymers of ethylene oxide and propylene oxide (for example of the Pluronic® type from BASF AG) is used as the covering material.

In particular, polyethylene glycols with a molecular weight of approx. 6000, fatty alcohol ethoxylates of the type Lutensol® AT from BASF AG (C ₁₆ -C ₁₈ fatty alcohol ethoxylates), ethylene oxide / propylene oxide block copolymers of the type Pluronic® PE 6 800 (ethylene oxide content approx. 80%, molecular weight approx. 8000) and stearic acid as the coating material.

Preferred substances of the formula (I) are those in which R ² and R ³ together with the nitrogen atom to which they are attached form a six-membered ring which may optionally contain a further N atom or an oxygen atom, and those in which R ¹ to R ^{3 are the} same or different and represent a C ₁ - to C ₄ -alkyl radical. The most preferred substances according to the present invention are N-methyl-morpholinium acetonitrile sulfate or hydrogen sulfate and trimethylammonium acetonitrile sulfate and hydrogen sulfate.

The coating can be applied from the melt or from solutions or Dispersions take place, the solvent or emulsifier being evaporated Will get removed. Also applied as a fine powder, for example by electrostatic Techniques is possible. The coating materials can be mixed, mixed and Granulators are applied to the granular N-alkylammonium acetonitrile. The coating materials are preferably applied in a fluidized bed, wherein the size of the particles can be classified at the same time. Should that Envelope materials can lead to sticky products under certain circumstances, it can be useful, the coated granular N-alkylammonium acetonitrile in addition to apply finely divided substances ("powdering"). Come as a powdering agent  all fine-particle substances in question, with other detergent components such as Builder substances can be used. Are preferred as additional Powdering agent zeolites, silicates, polycarboxylates, carbonates, citrates and starch used.

The amount of coating material used for that used according to the invention Bleach activator is 2 to 30% by weight based on the bleach activator basic granules containing. Preferred amounts of coating material are included Values of 5 to 20 wt .-%, in particular 5 to 15 wt .-%, each based on the Base granules.

Furthermore, it can be useful to achieve an optimal wrapping Temperature during the coating process in the area over a longer period of time to maintain the melting temperature in order to achieve an improved coating.

The average particle size of the coated granular N- Alkylammonium acetonitrile is in the range of 100 microns to 3000 microns, preferably in Range 300 µm to 2000 µm, most preferably 500 µm to 1200 µm.

The granular N-alkylammonium acetonitriles to be coated can also be in Combination with other bleach activators can be coated or used. these are for example compounds that are aliphatic under perhydrolysis conditions Peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. It acts it is often bleach activators that have one or more N or O acyl groups contain and / or carry optionally substituted benzoyl groups, such as substances from the class of anhydrides, esters, imides and acylated imidazoles or Oximes. Examples include tetracetylethylene diamine (TAED), tetraacetyl methylene diamine (TAMD), tetraacetylglycoluril (TAGU), tetraacetylhexylenediamine (TAHD), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonates (n- or iso-NOBS) and Lauroyloxybenzenesulfonate (LOBS), Pentaacetylglucose (PAG), 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine (DADHT) and isatoic anhydride (ISA).  

In combination with the coated granular N- Alkylammonium acetonitriles can also be bleach activators from the group consisting of carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2.5- Diacetoxy-2,5-dihydrofuran and those from German patent applications DE 196 16 693 and DE 196 16 767 known enol esters and acetylated sorbitol and mannitol or their mixtures described in European patent application EP 0 525 239 (SORMAN), acylated sugar derivatives, in particular pentaacetyl glucose (PAG), Pentaacetylfructose, tetraacetylxylose and octaacetyllactose, as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example, N-benzoylcaprolactam and carbonyl biscaprolactam, which are derived 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 are used bis (2-propylimino) carbonate, see DE-A 195 18 039, 195 41 012, 196 09 953 and 197 04 149.

Also suitable in combination with the coated granular materials according to the invention N-Alkylammoniumacetonitrilen from the German patent application DE 196 16 769 known hydrophilically substituted acylacetals and those in the German patent application DE 196 16 770 and international patent application WO 95/14075 Acyl lactams.

In addition to the conventional bleach activators listed above or other The place from the European patents EP-A 0 446 982 and EP-A 0 453 003 known sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes as so-called bleaching catalysts with the coated granular N-alkylammonium acetonitriles according to the invention combined become. The transition metal compounds in question include in particular the manganese, iron, known from German patent applications DE 195 29 905 Cobalt, ruthenium or molydane salt complexes and those from the German Patent application DE 196 20 267 known N-analog compounds, which from the German Patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or Molybdenum-carbonyl complexes, which are described in German patent application DE 196 05 688 described manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and Copper complexes with nitrogenous tripod ligands derived from the German  Patent application DE 196 20 411 known cobalt, iron, copper and Ruthenium-amine complexes, which are described in German patent application DE 44 16 438 Manganese, copper and cobalt complexes described in the European Patent application EP-A 0 272 030 described cobalt complexes, which from the European patent application EP-A 0 693 550 known manganese complexes, which from the European patent EP-A 0 392 592 known manganese, iron, cobalt and Copper complexes and / or those in European Patent EP-B 0 443 651 or European patent applications EP-A 0 458 397, EP-A 0 458 398, EP-A 0 549 271, Manganese complexes described in EP-A 0 549 272, EP-A 0 544 490 and EP-A 0 544 519.

In combination with the coated granular N- Alkylammonium acetonitriles can bleach-enhancing transition metal complexes, especially preferred with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru selected from the group of manganese and cobalt salts and complexes, especially preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the Cobalt (carbonyl) complexes, the chlorides of cobalt and manganese and Manganese sulfate can be selected. These bleach-enhancing transition metal complexes can in conventional amounts, preferably in an amount up to 5 wt .-%, in particular from 0.0025% by weight to 1% by weight and particularly preferably from 0.01% by weight to 0.25% by weight, each based on the entire detergent formulation.

Multi-acylated alkylenediamines are preferably used, in particular Tetraacetylethylenediamine (TAED), N-acylimides, especially N-nonanoylsuccinimide (NOSI), also glucose pentaacetate (GPA), xylose tetraacetate (TAX), Sodium 4-benzoyloxybenzenesulfonate (SBOBS), sodium trimethylhexanoyloxybenzene (STHOBS), tetraacetylglucoluril (TAGU), tetraacetylcyanoic acid (TACA), Di-N-acetyldimethylglyoxime (ADMG), 1-phenyl-3-acetylhydantoin (PAH), acylated Phenol sulfonates, nonanoyl benzene sulfonates (NOBS), isononanoyl benzene sulfonates (isoNOBS), Lauroylbenzenesulfonate (LOBS), Carbonylbiscaprolactam and Bis (2- Propylimino) carbonate.

The coated granular N-alkylammonium acetonitrile according to the invention are in generally used in combination with the bleaching agents listed below. Alkali metal perborates and their hydrates and alkali metal percarbonates, with preference Sodium perborate in the form of the mono- or tetrahydrate, or sodium percarbonate and whose hydrates are used. Persulfates and  Hydrogen peroxide and typical oxygen bleaches such as organic peracids, for example perbenzoic acid, peroxy-alpha-naphthoic acid, peroxylauric acid, Peroxystearic acid, phthalimidoperoxycaproic acid, nonylimidperoxysuccinic acid, Nonylimide peroxyadipic acid, 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelaic acid, Diperoxoisophthalic acid and 2-decyldiperoxybutane-1,4-diacid. Are also suitable cationic peroxyacids as described in patent applications US 5 422 028, US 5 294 362 and US Pat. No. 5,292,447, and sulfonyl peroxy acids, as described, for example, in of patent application US 5,039,447. Furthermore, the addition can be lower Quantities of bleach stabilizers such as phosphonates, borates, Metaborates, metasilicates and magnesium salts may be useful.

The peroxyacid bleaching agent is used in amounts equal to an amount of available oxygen between about 0.1% to about 10%, preferably between about 0.5% to about 5%, especially from about 1% to 4%. The percentages refer to the total weight of the detergent composition.

The proportion of the peroxide-containing bleaching agents in the inventive Detergent compositions are between about 0.1% to about 95% by weight and preferably between about 1% and about 60% by weight. If the Bleach composition also a fully formulated Detergent composition, it is preferred if the proportion of peroxide-containing bleaching agent is between about 1% by weight to about 20% by weight.

The N-alkylammonium acetonitriles coated according to the invention can also be used in combination with so-called bleach boosters. These are substances that further increase the effectiveness of the known bleaching agents. Particularly suitable bleach activators are the diamines described in DE-A 196 11 992. These are compounds which contain secondary amine groups - NHR ¹ and which are low molecular weight, oligomeric or polymeric. In particular, they are secondary amines of the general formula R ¹ NH - [(CR ³ R ⁴ ) _m -NH] _n -R ² (II), where n is an integer from 0 to 20 and m is an integer from 2 to 4, the radicals R ³ and R ^{4 are} independently C ₁ -C ₃₀ , preferably C ₁ -C ₁₅ hydrocarbyl radicals and the radicals R ¹ and R ^{2 are} independently C ₁ -C ₃₀ , preferably C ₁ -C ₁₅ - Are hydrocarbyl residues or, if necessary, together form a cycle. The bleaching power amplifiers disclosed in DE-A 196 11 992 are an integral part of the present invention and are incorporated into this by reference.

The N-alkylammonium acetonitrile salts coated according to the invention are in particular with the bleaching power amplifiers disclosed in the aforementioned application used. It gives particularly good results with regard to the effect of Combination of bleach activator / bleach booster obtained. It is of course under to name the achieved bleaching effect, which is particularly pronounced and therefore is principally desired. It has been shown that this bleaching effect in the case of Combination of the non-coated, described in the application DE 199 13 996 N-alkylammonium acetonitrile salts of the general formula (I) with bleach activator unwanted effects. The so-called pinhole spotting is closed call. This means point-like damage to dyed textile fabrics, which occur due to an undesired, premature partial hydrolysis of the salt (I), where it results in a local over-concentration of bleach activator / bleach booster comes and the damage from excessive local bleaching on the affected area entry. Such a pinhole spotting is achieved by the coating according to the invention avoided.

The granular N-alkylammonium acetonitriles coated according to the invention can be used as Bleach activators for use in detergents, cleaning agents, Dishwashing detergents, stain removers, disinfectants, denture cleaners, the Fiber bleaching such as B. the cellulose bleach, the pulp bleach or in the Cotton fiber bleach as well as hair bleach can be used. preferred Areas of application are detergents and dishwashing detergents.

The bleach activators are intended for each of these areas of application Formulations preferably in amounts up to 10% by weight, in particular 0.1% by weight 8% by weight, particularly 0.5 to 8% by weight and particularly preferably 0.8 to 5% by weight used on the entire formulation. The main areas of application are household and industrial laundry detergents and household and industrial Dishwashing formulations. The formulations in which the invention coated granular N-alkylammonium acetonitrile can be used exemplary for the application areas of textile detergents and machine dishwashers described below.

The coating of the invention makes the substances of the formula (I) light and safe to handle, dust formation is practically not observable. The  Substances are protected against undesirable hydrolysis, which for example easily enters detergent formulations.

Composition of household textile detergent

The detergent formulations in which the coated granular according to the invention N-alkylammonium acetonitrile can be used are powder, granules, paste, gel-like or liquid, or they are solid washing pieces. The formulations vary their intended use in their composition, the type of washing Adapt textiles. They contain conventional detergent ingredients that State of the art. Representative examples of such washing and Detergent ingredients are described below.

The total concentration of surfactants in the finished detergent formulation can be from 1 to 99 wt .-%, preferably from 5 to 80 wt .-%. The surfactants used can be anionic, nonionic, amphoteric or cationic. It can too Mixtures of the surfactants mentioned are used. preferred Detergent formulations contain anionic and / or nonionic surfactants and their mixtures with other surfactants.

Anionic surfactants are sulfates, sulfonates, carboxylates, phosphates and their Mixtures into consideration. Suitable cations are alkali metals such as for example sodium or potassium or alkaline earth metals, such as. B. calcium or Magnesium and ammonium, including substituted ammonium compounds Mono-, di- or triethanolammonium cations and mixtures thereof. Among the anionic surfactants are alkyl ester sulfonates, alkyl sulfates, alkyl ether sulfates, Alkyl benzene sulfonates, secondary alkane sulfonates and soaps are preferred. These will described below.

Alkyl ester sulfonates include linear esters of C ₁₈ -C ₂₀ carboxylic acids (fatty acids) which are sulfonated using gaseous SO ₃ , 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 B. tallow, coconut oil and palm oil, but also fats of a synthetic nature. Preferred alkyl ester sulfonates are compounds of the formula

wherein R ^{1 is} a C ₈ -C ₂₀ hydrocarbon radical, preferably alkyl, and R is a C ₁ -C ₆ hydrocarbon radical, preferably alkyl. M stands for a cation that forms a water-soluble salt with the alkyl ester sulfonate. Suitable cations are sodium, potassium, lithium or ammonium cations such as monoethanolamine, diethanolamine and triethanolamine. R ^{1 is} preferably C ₁₀ -C ₁₆ alkyl and R is methyl, ethyl or isopropyl. Most preferred are methyl ester sulfonates in which R ^{1 is} C ₁₀ -C ₁₆ alkyl.

Alkyl sulfates are water soluble salts or acids of the formula ROSO ₃ M wherein R is a C ₁₀ - C ₂₄ hydrocarbon group, preferably an alkyl or hydroxyalkyl radical having C ₁₀ -C ₂₀ - alkyl component, more preferably a C ₁₂ -C ₁₈ alkyl or Is hydroxyalkyl. M is hydrogen or a suitable cation, e.g. B. 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 alkylamines such as ethylamine, diethylamine and triethylamine Mixtures of quaternary ammonium cations derived therefrom. Alkyl chains with C ₁₂ -C ₁₆ are preferred for low washing temperatures (e.g. below approx. 50 ° C) and alkyl chains with C ₆ -C ₁₈ for higher washing temperatures (e.g. above approx. 50 ° C).

Alkyl ether sulfates are water-soluble salts or acids of the formula RO (A) _m SO ₃ M, where R is an unsubstituted C ₁₀ -C ₂₄ -alkyl or hydroxyalkyl radical, preferably a C ₁₂ -C ₂₀ -alkyl or hydroxyalkyl radical, particularly preferably a C ₁₂ -C _{18 represents} alkyl or hydroxyalkyl. A is an ethoxy or propoxy unit, m is a number greater than 0, preferably between approximately 0.5 and approximately 6, particularly preferably between approximately 0.5 and approximately 3, and M is a hydrogen atom or a cation such as, for , 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 as well as those derived from alkylamines such as ethylamine, diethylamine, triethylamine or mixtures thereof. Examples include C ₁₂ -C ₁₈ fatty alcohol ether sulfates, the content of ethylene oxide units being 1, 2, 2.5, 3 or 4 mol per mol of the fatty alcohol ether sulfate and in which M is sodium or potassium.

In secondary alkanesulfonates, the alkyl group can either be saturated or unsaturated, be branched or linear and optionally substituted with a hydroxyl group. The Sulfo group can be at any position on the C chain, the primary Methyl groups at the beginning and end of the chain have no sulfonate groups. The preferred secondary alkanesulfonates contain linear alkyl chains with about 9 to 25 Carbon atoms, preferably about 10 to about 20 carbon atoms and especially 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 as the cation is preferred.

Other suitable anionic surfactants are alkenyl or alkylbenzenesulfonates. The Alkenyl or alkyl group can be branched or linear and optionally with a hydroxyl group be substituted. The preferred alkylbenzenesulfonates contain linear alkyl chains about 9 to 25 carbon atoms, preferably from about 10 to about 13 carbon atoms, that Cation is sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof. Magnesium is considered for mild surfactant systems Cation preferred, but sodium for standard washing applications. The same applies to Alkenylbenzenesulfonates.

The term anionic surfactants also includes olefin sulfonates which are obtained by sulfonating C ₁₂ -C ₂₄ , preferably C ₁₄ -C ₁₆ α-olefins with sulfur trioxide and subsequent neutralization. Due to the manufacturing process, these olefin sulfonates can contain smaller amounts of hydroxyalkanesulfonates and alkane disulfonates. Special mixtures of α-olefin sulfonates are described in US 3,332,880.

Other preferred anionic surfactants are carboxylates, e.g. B. fatty acid soaps and comparable surfactants. The soaps can and can be saturated or unsaturated contain various substituents such as hydroxyl groups or α-sulfonate groups. Linear saturated or unsaturated hydrocarbon radicals are preferred as hydrophobic Portion with about 6 to about 30, preferably about 10 to about 18 carbon atoms.  

Other suitable anionic surfactants are: salts of acylaminocarboxylic acids; the acyl sarcosinates formed by the reaction of 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 -C ₂₄ olefin sulfonates; sulfonated polycarboxylic acids, prepared by sulfonation of the pyrolysis products of alkaline earth metal citrates, such as. B. described in GB-1,082,179; alkylglycerol; acylglycerol sulfates; alkylphenol; primary paraffin sulfonates; alkyl phosphates; alkyl ether; Isethionates such as acyl isethionates; N-acyl taurides; alkyl succinates; sulfosuccinates; Monoesters of sulfosuccinates (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C ₁₂ -C ₁₈ diesters); acyl sarcosinates; Sulfates of alkyl polysaccharides such as sulfates of alkyl polyglycosides, branched primary alkyl sulfates and alkyl polyethoxy carboxylates such as those of the formula RO (CH ₂ CH ₂ ) _k CH ₂ COO ^- M ⁺ , where RC ₈ to C ₂₂ alkyl, k is a number from 0 to 10 and M is a cation; Resin acids or hydrogenated resin acids such as 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).

The following compounds are suitable as nonionic surfactants, for example:

• - Polyethylene, polypropylene and polybutylene oxide condensates of alkyphenols.

These compounds include the condensation products of alkylphenols with a C ₆ -C ₂₀ alkyl group, which can be either linear or branched, with alkene oxides. Compounds with about 5 to 25 mol of alkene oxide per mol of alkylphenol are preferred.

• - Condensation products of aliphatic alcohols with approx. 1 to approx. 25 mol Ethylene oxide.

The alkyl chain of the aliphatic alcohols can be linear or branched, primary or secondary and generally contains from about 8 to about 22 carbon atoms. The condensation products of C ₁₀ to C ₂₀ alcohols with about 2 to about 18 moles of ethylene oxide per mole of alcohol are particularly preferred. The alkyl chain can be saturated or unsaturated. The alcohol ethoxylates can have a narrow ("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® brands from BASF Aktiengesellschaft.

• - Condensation products of ethylene oxide with a hydrophobic base by condensation of propylene oxide with propylene glycol.

The hydrophobic part of these compounds preferably has a molecular weight between approximately 1,500 and approximately 1,800. The attachment of ethylene oxide to this Hydrophobic part leads to an improvement in water solubility. The product is liquid up to a polyoxyethylene content of approx. 50% of the total weight of the Condensation product, which is a condensation with up to about 40 mol of ethylene oxide equivalent. Examples of this product class that are commercially available are Pluronic® brands 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 Ethylene diamine with excess propylene oxide and generally has Molecular weight from about 2,500 to 3,000. At this hydrophobic unit Ethylene oxide up to a content of about 40 to about 80 wt .-% polyoxyethylene and one Molecular weight of approximately 5,000 to 11,000 added. Commercially available examples This class of compounds includes the Tetronic® brands 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 with an alkyl radical of approximately 10 to approximately 18 carbon atoms. Semipolar nonionic surfactants are also amine oxides of the formula

R is an alkyl, hydroxyalkyl or alkylphenol group with a chain length of about 8 to about 22 carbon atoms. R ² is an alkylene or hydroxyalkylene group with about 2 to 3 carbon atoms or mixtures thereof, each radical R ¹ is an alkyl or hydroxyalkyl group with about 1 to about 3 carbon atoms or a polyethylene oxide group with about 1 to about 3 ethylene oxide units , and x denotes a number from 0 to about 10. The R ¹ groups can be connected to one another via an oxygen or nitrogen atom and thus form a ring. Amine oxides of this type are in particular C ₁₀ -C ₁₈ -alkyldimethylamine oxides and C ₈ -C ₁₂ - alkoxyethyl-dihydroxyethylamine oxides.

• - fatty acid amides

Fatty acid amides have the formula

wherein R is an alkyl group with about 7 to about 21, preferably about 9 to about 17 carbon atoms and R ^{1 is} independently hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl or (C ₂ H ₄ O) _x H means, where x varies from about 1 to about 3. C ₈ -C ₂₀ amides, monoethanolamides, diethanolamides and isopropanolamides are preferred.

Other suitable nonionic surfactants are alkyl and alkenyl oligoglycosides as well Fatty acid polyglycol esters or fatty amine polyglycol esters, each with 8 to 20, preferably 12 to 18 carbon atoms in the fatty alkyl radical, alkoxylated triglycamides, mixed ethers or Mixed forms, alkyl oligoglycosides, alkenyl oligoglycosides, fatty acid N-alkyl glucamides, Phosphine oxides, dialkyl sulfoxides and protein hydrolyzates.  

Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkylamide betaines, aminopropionates, aminoglycinates or amphoteric imidazolinium compounds of the formula

wherein R ^{1 is} C ₈ -C ₂₂ alkyl or alkenyl, R _{2 is} hydrogen or CH ₂ CO ₂ M, R ³ CH ₂ CH ₂ OH or CH ₂ CH ₂ OCH ₂ CH ₂ CO ₂ M, R ^{4 is} hydrogen, CH ₂ CH ₂ OH or CH ₂ CH ₂ COOM, Z CO ₂ M or CH ₂ CO ₂ M, n 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 include cocoamphocarboxypropionate, cocoamidocarboxypropionic acid, Cocoamphocarboxyglycinate (also known as cocoamphodiacetate) and Cocoamphoacetate.

Further preferred amphoteric surfactants are alkyldimethylbetaines and Alkyldipolyethoxybetaines with an alkyl radical having about 8 to about 22 carbon atoms, the can be linear or branched, preferably with 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 ¹ N (CH ₃ ) ₃ ⁺ X ^- , R ¹ R ² N (CH ₃ ) ₂ ⁺ X ^- , R ¹ R ² R ³ N (CH ₃ ) ⁺ X ^- or R ¹ R ² R ³ R ⁴ N ⁺ X ^- . The radicals R ¹ , R ² , R ³ and R ⁴ are, independently of one another, preferably unsubstituted alkyl with a chain length of 8 to 24 carbon atoms, in particular of 10 to 18 carbon atoms, hydroxyalkyl with 1 to 4 carbon atoms, phenyl, C ₂ -C ₁₈ alkenyl, C ₇ -C ₂₄ aralkyl, (C ₂ H ₄ O) _x H, where x is an integer from 1 to 3, be one or more alkyl groups containing ester groups or cyclic quaternary ammonium salts. X is a suitable anion known to those skilled in the art.

Other laundry detergent and cleaning agent ingredients used in the present invention may include inorganic and / or organic builders to the To reduce the hardness of the water.

These builders can range from about 5% to about 80% by weight Detergent and cleaning agent compositions may be included. inorganic Builders include, for example, alkali, ammonium and alkanolammonium salts of polyphosphates such as tripolyphosphates, pyrophosphates and glassy 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 : Na ₂ O ratio between 1.6: 1 and 3.2: 1, and sheet silicates, for example the sodium sheet silicates described in US Pat. No. 4,664,839, available from Clariant GmbH under the brand name SKS®. SKS-6® is a particularly preferred layered silicate builder.

Aluminosilicate builders are particularly preferred for the present invention. These are in particular zeolites with the formula Na _z [(AlO ₂ ) _z (SiO ₂ ) _y ] .xH ₂ O, where z and y are integers of at least 6, the ratio of z to y of about 1, 0 to 0.5 and x is an integer from 15 to 264.

Suitable ion exchangers based on aluminosilicate are commercially available. This Aluminosilicates can be crystalline or amorphous in structure and can be natural occurring or also synthetically manufactured. Process for the production of Ion exchangers based on aluminosilicate are described for example in U.S. 3,985,669 and U.S. 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. Preferred Aluminosilicates with a particle diameter between 0.1 and 10 µm.

Suitable organic builders include polycarboxyl compounds such as Ether polycarboxylates and oxydisuccinates, such as in US-3,128,287 and US 3,635,830. Also known from US-4,663,071 are TMS / TDS Suitable for builders.  

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, Ammonium and substituted ammonium salts of polyacetic acids such as. B. Ethylenediaminetetraacetic acid and nitrilotriacetic acid as well as polycarboxylic acids such as Mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxy succinic acid and their soluble salts.

Citrate-based builders, e.g. B. citric acid and its soluble salts, especially that Sodium salt, are preferred polycarboxylic acid builders, which are also in granulated Formulations, especially together with zeolites and / or layered silicates can be used.

Other suitable builders are the 3,3-dicarboxy-4-oxa-1,6-hexanedioate and related compounds disclosed in US 4,566,984.

If phosphorus-based builders can be used, and especially if Soap bars for laundry to be formulated by hand can be different Alkali metal phosphates such as sodium tripolyphosphate, sodium pyrophosphate and Sodium orthophosphate can be used. Phosphonate builders such as Ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates as they for example, in U.S. 3,159,581, U.S. 3,213,030, U.S. 3,422,021, U.S. 3,400,148 and U.S. 3,422,137 are used.

In general, the salts of the formula (I) coated with the invention used detergent ingredients from typical for detergents Components such as surfactants and builders can be selected. If necessary, the detergent ingredients can contain one or more Cleaning aids or other materials contain the cleaning effect reinforce, serve for the treatment or care of the object to be cleaned or the Change the usage properties of the detergent composition. suitable Cleaning aids in detergent compositions include, for example the substances mentioned in US-3,936,537. The cleaning aids used in the Detergent compositions of the present invention can be used include, for example, enzymes, in particular proteases, lipases and cellulases, Foam booster, foam brake, start-up and / or anti-corrosion agent,  Suspending agents, dyes, fillers, optical brighteners, disinfectants, Alkalis, hydrotropic compounds, antioxidants, enzyme stabilizers, perfumes, Solvents, solubilizers, redeposition inhibitors, dispersants, Color transfer inhibitors, e.g. B. Polyamine N-oxides such as Poly (4-vinylpyridine-N-oxide), polyvinylpyrrolidone, poly-N-vinyl-N-methylacetamide and Copolymers of N-vinylimidazole and N-vinylpyrrolidone, processing aids, Plasticizers and anti-static agents.

Typical bleaching agents, such as those coated in combination with the inventive granular N-alkylammonium acetonitriles are described above.

The detergent compositions can be coated in addition to those of the invention granular N-alkylammonium acetonitriles one or more conventional enzymes, such as Contain 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 optimal pH range between 5 and 9.5. suitable Cellulases are disclosed in US 4,435,307. It is cellulase made by a strain of Humicola insolens is produced, in particular the Humicola strain DSM 1800 or another cellulase-212-producing mushroom belonging to the genus Aeromonas also belongs to Cellulase, which comes from the hepatopancreas of certain marine species Molluscs was extracted. Suitable cellulases are also in GB-A-2.075.028, GB-A-2.085.27 and DE-OS-2.247.832.

Preferred cellulases are described in WO-91/17243. The invention Detergent compositions contain enzymes in amounts up to about 50 mg, preferably from about 0.01 mg to about 10 mg per gram of Detergent composition. Based on the weight of the Detergent compositions contain at least 0.001% by weight of the enzymes, preferably between about 0.001% by weight to about 5% by weight, in particular from from about 0.001% to about 1%, especially from about 0.01% to about 1% by weight.  

Composition of machine dishwashers Builder

Water-soluble and water-insoluble builders can be used, their The main task is to bind calcium and magnesium. Usual builders who between 10 and 90% by weight, based on the total preparation, can be present, are listed below.

Phosphates such as alkali phosphates and polymeric alkali phosphates, which are in the form their alkaline, neutral or acidic sodium or potassium salts may be present. Examples include trisodium phosphate, tetrasodium diphosphate, Disodium dihydrogen phosphate, pentasodium tripolyphosphate, so-called Sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization from 5 to 1000, in particular from 5 to 50, and the corresponding potassium salts or Mixtures of sodium hexametaphosphate and the corresponding potassium salts or Mixtures of sodium and potassium salts. These phosphates are preferably in Range from 25 wt .-% to 65 wt .-% based on the entire recipe and calculated used as an anhydrous active substance.

Low molecular weight carboxylic acids and their salts, such as. B. alkali citrates (such as anhydrous trisodium citrate or trisodium citrate dihydrate), alkali succinates, Alkali mononates, fatty acid sulfonates, oxydisuccinate, 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 B. polyacrylic acid, polymethacrylic acid, copolymer maleic acid / acrylic acid, Copolymer maleic acid / acrylic acid / vinyl acetate; Graft polymers from monoethylenic unsaturated mono- and / or dicarboxylic acids on monosaccharides, oligosaccharides, Polysaccharides or polyaspartic acid; Aminopolycarboxylates and polyaspartic acid; Carbonates such as sodium carbonate and sodium bicarbonate.

Complexing agents and phosphonates and their salts, such as. B. nitrilotriacetic acid, Ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylene diaminetriacetic acid, methylglycinediacetic acid, 2-phosphono-1,2,4-butane tricarboxylic acid, Aminotri- (methylenephosphonic acid), 1-hydroxyethylene (1,1-diphosphonic acid), ethylenedi amine tetramethylene phosphonic acid, hexamethylene diamine tetramethylene phosphonic acid and diethylenetriamine-pentamethylene-phosphonic acid.  

Silicates such as sodium disilicate and sodium metasilicate. Water-insoluble builders include the zeolites and crystalline layered silicates, the latter in particular corresponding to the general formula NaMSi _x O _{2x + 1} .y H ₂ O, where M represents 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 of this are in particular (α-Na ₂ Si ₂ O ₅ , β-Na ₂ Si ₂ O ₅ , δ-Na ₂ Si ₂ O _5. Also included are mixtures of the abovementioned builder substances. Trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders from the class of disilicates and / or metasilicates.

alkali carriers

Alkali carriers can be present as further constituents. As an alkali carrier apply alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, Alkali metal sesquicarbonates, alkali silicates, alkali metal silicates and mixtures of aforementioned substances, preferably the alkali carbonates, in particular sodium carbonate, Sodium bicarbonate or sodium sesquicarbonate can be used. preferred Combinations of builder and alkali carrier are mixtures of tripolyphosphate and Sodium carbonate or tripolyphosphate, sodium carbonate and sodium disilicate.

surfactants

Low or low-foaming nonionic surfactants are preferred in Proportions of 0.1 to 20% by weight (preferably 0.1-10% by weight, 0.25-4% by weight) used. These are, for example, surfactants from the group of fatty alcohol ethoxylates, such as they z. B. commercially under the product names Plurafac® (BASF Aktiengesellschaft) or Dehypon® (Cognis) are available. Furthermore, Di- and Multiblock copolymers composed of ethylene oxide and propylene oxide are used, as for example under the name Pluronic® (BASF Aktiengesellschaft) or Tetronic® (BASF Corporation) are commercially available. Can continue Reaction products from sorbitan esters with ethylene oxide and / or propylene oxide be used. Amine oxides or alkyl glycosides are also suitable. An overview Suitable nonionic surfactants are, for example, EP-A 0851 023 and DE-A 198 19 187.

The formulation can also contain anionic or zwitterionic surfactants, preferably mixed with nonionic surfactants. Suitable anionic and  zwitterionic surfactants are also in the documents EP-A 0 851 023 and Called DE-A 198 19 187.

Typical bleaching agents in combination with the salts used according to the invention of formula (I) can be used are described above.

corrosion inhibitors

In particular, silver protection agents 1 from the group of Triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the Alkylaminotriazoles and the transition metal salts or complex are used. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. you often finds active chlorine-containing agents in detergent formulations Can significantly reduce corroding of the silver surface. In chlorine-free cleaners preference is given to oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, Hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives thereof Connection classes used. Also salt and complex inorganic Compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often found Use. The transition metal salts selected from are preferred the group of manganese and cobalt salts and their complexes, particularly preferably the Cobalt (ammin) complexes, the cobalt (acetate) complexes, the Cobalt (carbonyl) complexes, the chlorides of cobalt and manganese and Manganese sulfate. Zinc compounds or bismuth compounds can also be used Prevention of corrosion on the wash ware.

enzymes

The cleaning agent can contain between 0 and 5% by weight of enzymes All of the preparation can be added to the performance of the cleaners increase or under milder conditions the cleaning performance of the same quality guarantee. The most commonly used enzymes include lipases, amylases, Cellulases and proteases. Esterases, pectinases, lactases and Peroxidases are used. Preferred proteases are e.g. B. 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. Cellulases and lipases are particularly suitable Celluzym® 0.7 T and Lipolase® 30 T from Novo Nordisk. Special use as Amamases are found in 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. Other enzymes can also be used.

Other additives

Paraffin oils and silicone oils can optionally be used as defoamers and for Protection of plastic and metal surfaces can be used. Become a defoamer generally dosed in proportions of 0.001% to 5%.

The coated granular N-alkylammonium acetonitrile according to the invention can in Detergent formulations for both the household and the commercial Area can be used. Commercial types of cleaners usually contain a builder system based on pentasodium triphosphate, and / or sodium citrate and / or complexing agents such as B., nitrilotriacetate. In contrast to household cleaners, caustic soda is often used or potash lye worked as an alkali carrier.

The coated granular N-alkylammonium acetonitriles according to the invention can both in liquid, gel, powder, granular and tablet form Dishwashers are used. It is possible to coated the invention granular N-alkylammonium acetonitriles if necessary with other formulation components in incorporate special compartments such as B. microcapsules, gel capsules. Furthermore the copolymers according to the invention can also be used in special compartments be installed inside dishwasher detergent tablets, which may be opposite the other tablet compartments can show different dissolution behavior. This can be both certain tablet layers, as well as certain in the tablet molded articles that are embedded, glued to the tablet or enveloped by the tablet.

The invention will now be explained in the following examples. They have Abbreviations the meaning known to the expert.  

Examples example 1 Production of granular N-methylmorpholinium acetonitrile hydrogen sulfate (MMA)

60 liters of a 65% strength by weight aqueous solution were placed in an 80 liter glass container submitted by N-methylmorpholinium acetonitrile methyl sulfate. The solution was on Heated to 110 ° C and at a pressure of 600 mbar over a period of 3 hours evaporated. The melt, which contains N-methylmorpholinium acetonitrile Hydrogen sulfate had about 80 wt .-% (the rest consisted essentially of inorganic salts and water), was then in one 160 liter Lödige mixer applied to 16 kg of a commercially available silica and the Mixture froze. The solidified mixture was then reduced to a particle size of 350 to 1600 microns sieved. The coarse material was larger than 1600 microns ground and then sieved again. So a granular granulate with one Obtained content of about 60 wt .-% of N-methylmorpholinium actorlitrile hydrogensuifat.

Example 2 Granular Trimethylammonium Acetonitrile Hydrogen Sulphate (TMAQ) Preparation

60 liters of a 48% by weight aqueous solution were placed in an 80 liter glass container submitted by trimethylarmonium acetonitrile methyl sulfate. The solution was at 110 ° C heated and at a pressure of 500 mbar over a period of 4 hours evaporated. The melt gives way to a content of trimethylammonium aceto nitrile hydrogen sulfate of about 80 wt .-% (the rest consisted essentially of inorganic salts and water), was then in one 160 liter Lödige mixer applied to 12 kg of a commercially available silica and the Mixture froze. The solidified mixture was then reduced to a particle size of 350 to 1600 microns sieved. The coarse material was larger than 1600 microns ground and then sieved again. So a granular granulate with one Obtained content of about 60 wt .-% of N-methylmorpholinium actonitrile hydrogen sulfate.

Example 3 Coating of granular N-methylmorpholinium acetonitrile hydrogen sulfate with Polyethylene glycol Mw 6000 (15% load)

2 kg of granular N-methylmorpholinium were placed in a laboratory spray fluidized bed Submitted acetonitrile hydrogen sulfate and swirled with air at room temperature. In a heated storage container were given 300 g of solid polyethylene glycol Mw 6000 and melted at a temperature of 80 ° C. The melt was heated over a Sprayed nozzle into the fluidized bed over a period of 30 minutes and so the swirling methylmorpholinium acetonitrile hydrogen sulfate granules coated.

Example 4 Coating of granular trimethylammonium acetonitrile hydrogen sulfate with a aqueous dispersion of a copolymer of ethyl acrylate and methacrylic acid (weight ratio 1: 1, Mw 250000) (10% load)

2 kg of trimethylammonium were placed in a laboratory spray fluidized bed Acetonitrile hydrogen sulfate presented and swirled with air at 65 ° C. In a stirred Storage containers were made from 1 kg of an aqueous dispersion of a copolymer Ethyl acrylate and methacrylic acid (solids content 20 mass%) submitted. after the Fluidized bed had reached a temperature of 50 ° C, the dispersion was over a Sprayed for a period of 2.5 hours. After spraying, the coated ones Granules at an air temperature of 40 ° C for a period of 30 minutes dried.

Example 5 Coating of granular trimethylammonium acetonitrile hydrogen sulfate with Stearic acid (10% load)

2 kg of trimethylammonium were placed in a laboratory spray fluidized bed Submitted acetonitrile hydrogen sulfate and swirled with air at room temperature. In a heated storage container were placed in 200 g of solid stearic acid and with stirring melted at a temperature of 85 ° C. The melt was passed through a heated nozzle sprayed into the fluidized bed over a period of 45 minutes.  

Examples 6-15 were coated analogously to examples 3-5:

Checking the spotting behavior method

6 colored fabrics (reactive red 21 on cotton) measuring 10 cm × 10 cm are made in placed a flat plastic tub measuring 30 cm × 50 cm and with a Metal grid measuring 25 cm × 45 cm (hole diameter 5 mm) covered. In the Tub, 250 ml tap water (temperature 21 ° C, water hardness 3.5 mmol / l) given so that the tissues are completely covered. 5 g of each tissue Detergent formulation applied evenly. At 21 ° C you leave the damp Apply detergent to the fabric for 10 minutes. After that, the tissue rinsed with tap water and dried.  

Spotting damage is assessed visually on the following scale:

test formulation

The detergent formulation used to test the spotting behavior is composed as follows:

test results

Stability in an alkaline cleaner formulation method

10 g of the cleaner formulation below were placed in a climatic chamber at 25 ° C and 70% relative humidity stored open for 3 weeks. Then the analytical determination of the non-hydrolyzed bleach activator by means of HPLC. from that the percentage of the unchanged bleach activator was based on the Initial activator content taking into account the proportion of coating material calculated.  

detergent formulation

test results

Claims (12)

1. Granular, coated N-alkylammonium acetonitrile salt of the general formula (I)
R ² R ³ NR ¹ -CR ⁴ R ⁵ -CN ⁺ Y ^- (I)
in the
R ^{1 is} a C ₁ to C ₂₄ alkyl group which can be interrupted by non-adjacent oxygen atoms or can additionally carry hydroxyl groups, a C ₄ to C ₂ cycloalkyl group, a C ₇ to C ₂₄ alkaryl group or a grouping of the formula - CR ⁴ R ⁵ -CN means
R ² and R ³ each independently of one another have the meaning of R ¹ or together represent a saturated four- to nine-membered ring with at least one carbon atom and at least one further hetero atom from the group consisting of oxygen, sulfur and nitrogen,
R ⁴ and R ⁵ each independently of one another are hydrogen, a C ₁ to C ₂₄ alkyl group which can be interrupted by non-adjacent oxygen atoms or can additionally carry hydroxyl groups, a C ₄ to C ₂₄ cycloalkyl group or a C ₇ to C ₂₄ -Alkaryl group means and
Y represents a sulfate or bisulfate anion of the corresponding stoichiometric amount,
wherein the salts of formula (I) are coated with a material which is selected from the group consisting of organic, inorganic, hydrophilic and hydrophobic substances. 2. Granular, coated N-alkylammonium acetonitrile salt according to claim 1, characterized in that the coating materials are selected from the group consisting of fatty alcohols, fatty alcohol / ammonium stearate mixtures, ethoxylated fatty alcohols, in particular C ₈ -C ₃₁ fatty alcohol polyalkoxylates with 1 to 150 Moles of ethylene oxide, ethoxylated oxo alcohols, fatty acids, especially 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, montanic acid waxes, polyethylene waxes, oxidized polyethylene waxes, ethylene / acrylic acid copolymer Waxes, ethylene / vinyl acetate copolymer waxes, polyalkyl vinyl ether waxes, dispersions of 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. Grainy, coated N-alkylammonium acetonitrile salt according to claim 1, characterized in that the inorganic coating material is selected from the group consisting of magnesium sulfate, sodium hexaphosphate, Dihydrogen phosphate, pyrophosphate, phosphonic acids, sodium metaborate, Sodium metasilicate, water glass, sodium polyphosphate, sodium sulfate, Sodium carbonate, sodium silicate, sodium bicarbonate, borax, magnesium sulfate and Boric acid. 4. Granular, coated N-alkylammonium acetonitrile salt according to claim 1, characterized in that the organic, hydrophilic coating material is selected from the group consisting of polyethylene glycols with a Molecular weight from 1000 to 50,000 and block copolymers and statistical Copolymers of ethylene glycol and propylene glycol. 5. Granular, coated N-alkylammonium acetonitrile salt according to one of claims 1 to 4, characterized in that the coating material is selected from the group consisting of polyethylene glycols with a molecular weight ≧ 1500, 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 with a molecular weight of approx. 6000, fatty alcohol ethoxylates of C ₁₆ -C ₁₈ fatty alcohols, ethylene oxide / propylene oxide block copolymers with an ethylene oxide content of approx. 80% and a molecular weight of approx. 8000, and stearic acid. 6. Granular, coated N-alkylammonium acetonitrile salt according to any one of claims 1 to 5, characterized in that R ² and R ³ together with the nitrogen atom to which they are attached form a six-membered ring, which optionally has a further nitrogen atom or an oxygen atom may contain, form or R ¹ to R ^{3 are the} same or different and represent a C ₁ -C ₄ alkyl radical, in particular N-methyl morpholinium acetonitrile sulfate or hydrogen sulfate or trimethyl ammonium acetonitrile sulfate or hydrogen sulfate. 7. Granular, coated N-alkylammonium acetonitrile salt according to one of the Claims 1 to 6, characterized in that this in combination with others Bleach activators are used, preferably multiple acylated Alkylenediamines, especially tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), glucose pentaacetate (GPA), Xylose tetraacetate (TAX), sodium 4-benzoyloxybenzenesulfonate (SBOBS), Sodium trimethylhexanoyloxybenzene (STHOBS), tetraacetylglucoluril (TAGU), Tetraacetylcyanoic acid (TACA), di-N-acetyldimethylglyoxime (ADMG), 1-phenyl-3-acetylhydantoin (PAH), acylated phenol sulfonates, Nonanoylbenzenesulfonates (NOBS), isononanoylbenzenesulfonates (isoNOBS), Lauroylbenzenesulfonates (LOBS), Carbonylbiscaprolactam and / or Bis (2- Propylimino) carbonate. 8. Granular, coated N-alkylammonium acetonitrile salt according to one of claims 1 to 7, characterized in that this is used in combination with a bleaching power booster, preferably a bleaching power booster composed of a low molecular weight, oligomeric or polymeric compound containing secondary amine group NHRt, in particular from the group consisting of secondary amines of the general formula
R ¹ NH - [(CR ³ R ⁴ ) _m -NH] NR ² , (II)
wherein N has an integer value from 0 to 20 and m has an integer value from 2 to 4, the radicals R ³ and R ^{4 are} independently of one another C ₁ -C ₃₀ , preferably C ₁ - C ₁₅ hydrocarbyl radicals and the radicals R ¹ and R ^{2 are,} independently of one another, C ₁ -C ₃₀ , preferably C ₁ -C ₁₅ hydrocarbyl radicals which, if appropriate, together form a cyclic radical. 9. Grainy, coated N-alkyl ammonium acetonitrile salt according to one of the Claims 1 to 8, characterized in that this together with bleaching agents from the group consisting of alkali metal perborates and their hydrates, Alkali metal percarbonates, especially sodium perborate in the form of the mono- or Tetrahydrate, sodium percarbonate and its hydrates, persulfates, Hydrogen peroxide, oxygen bleaches, preferably organic peracids, in particular perbenzoic acid, peroxy-alpha-naphthoic acid, peroxylauric acid, Peroxystearic acid, phthalimidoperoxycaproic acid, nonylimidperoxysuccinic acid, Nonylimide peroxyadipic acid, 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelaine acid, diperoxoisophthalic acid, and 2-decyldiperoxybutane-1,4-diacid, cationic Peroxyacids and sulfonylperoxyacids are used. 10. Process for making a granular, coated N-alkyl ammonium acetonitrile salt according to one of claims 1 to 9, characterized in that a suitable coating material from the melt, solution or dispersion with removal of the solvent or dispersant by evaporation or in Form of a fine powder is applied, preferably by applying the Envelope materials in a fluidized bed. 11. bleach activator containing at least one granular, coated N-alkylammonium acetonitrile salt according to one of claims 1 to 9. 12. Detergents, cleaning agents, dishwashing detergents, stain remover, Disinfectants, denture cleaners, 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, containing at least one granular, coated N-alkylammonium acetonitrile salt according to one of claims 1 to 9.