DE102019217850A1 - Bleach activator with a cationic group and detergent or cleaning agent containing it II - Google Patents

Abstract

The oxidizing and bleaching action of peroxygen compounds at low temperatures should be improved. This was essentially achieved through the use of organic peroxo acids under perhydrolysis conditions with compounds which form cationic groups and in which the leaving group is cyclic and contains at least 2 heteroatoms.

Description

The present invention relates to certain cationic organic peracid-forming compounds under perhydrolysis conditions, their use for activating peroxygen compounds in connection with the bleaching of soiling when washing textiles and cleaning hard surfaces, as well as detergents and cleaning agents containing them.

Inorganic peroxygen compounds, in particular hydrogen peroxide and solid peroxygen compounds which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes. The oxidizing effect of these substances depends strongly on the temperature in dilute solutions; for example, with H ₂ O ₂ or alkali perborate in alkaline bleaching liquors, sufficiently rapid bleaching of soiled textiles is only achieved at temperatures above about 80 ° C. At lower temperatures, the oxidizing effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, which are able to deliver peroxocarboxylic acids under the perhydrolysis conditions mentioned and for which numerous proposals, especially from the classes of N- or O-acyl compounds, for example several times acylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulphurylamides and cyanurates, also carboxylic acid anhydrides, especially sodium anhydrides, sodium anhydride anhydrides, especially sodium anhydride anhydrides, especially sodium anhydride anhydrides, especially sodium anhydride anhydrides, especially sodium anhydride anhydrides, especially sodium anhydride anhydrides, especially sodium anhydride anhydrides, especially sodium anhydride anhydride, especially isononanoyloxy-benzenesulfonate, O-acylated sugar derivatives, such as pentaacetylglucose, and N-acylated lactams, such as N-benzoylcaprolactam, have become known in the literature. By adding these substances, the bleaching effect of aqueous peroxide liquors can be increased to such an extent that essentially the same effects occur at temperatures around 60 ° C as with the peroxide liquor alone at 95 ° C.

In the endeavor to achieve energy-saving washing and bleaching processes, application temperatures well below 60 ° C, in particular below 45 ° C down to the cold water temperature, have become more important in recent years.

At low temperatures, the activity of the previously known activator compounds generally diminishes noticeably.

From the international patent application WO 96/06915 A1 bleach activators are known which, under perhydrolysis conditions, form organic peroxo acids with a cationic group.

Surprisingly, it has now been found that, under perhydrolysis conditions, organic peroxyacids with cationic group-forming compounds with cyclic leaving group with at least 2 heteroatoms are particularly suitable for enhancing the bleaching effect of peroxygen-containing detergents and cleaning agents.

in der
A für O, S, Se;
Z für einen gegebenenfalls substituierten C_1-30 Alkylen-, C_3-30 Cycloalkylen-, Arylen-, Alkylenarylen- oder Arylenalkylen-Rest;
X für ein Anion, insbesondere Chlorid, Bromid, Iodid, Tosylat, Mesylat, Triflat, Sulfat, Carbonat und/oder Phosphat;
Y für NR⁸, O, S, Se, C(R⁸)₂;
R¹, R², R³, R⁴, R⁵ und R⁸ unabhängig voneinander für H, einen C_1-30 Alkyl-, C_3-30 Cycloalkyl-, Aryl-, Alkylaryl- oder Arylalkyl-Rest, wobei zwei oder mehrere der Reste R³, R⁴ und R⁵ auch miteinander verbunden sein können und einen genannten Cylcloalkyl- oder Aryl-Rest bilden; und n für eine Zahl im Bereich von 1 bis 12 stehen.The invention therefore provides a bleach-activating compound of the general formula (I),

in the
A for O, S, Se;
Z represents an optionally substituted C _1-30 alkylene, C _3-30 cycloalkylene, arylene, alkylenearylene or arylenealkylene radical;
X for an anion, in particular chloride, bromide, iodide, tosylate, mesylate, triflate, sulfate, carbonate and / or phosphate;
Y is NR ⁸ , O, S, Se, C (R ⁸ ) ₂ ;
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁸ independently of one another represent H, a C _1-30 alkyl, C _3-30 cycloalkyl, aryl, alkylaryl or arylalkyl radical, where two or several of the radicals R ³ , R ⁴ and R ^{5 can} also be connected to one another and form a stated cycloalkyl or aryl radical; and n is a number in the range from 1 to 12.

In the specified hydrocarbon radicals, 1 or more non-adjacent carbon atoms not bonded to a heteroatom can be replaced by a heteroatom, in particular N, O, S and / or Se. If X ^{- is} a polyvalent anion, correspondingly several of the units containing the quaternary nitrogen atom, which form the remaining part of the compound according to formula (I), are present ^{per anion X -.} Preferably R ¹ , R ² , R ³ , R ⁴ , R ⁵ and / or R ^{8 are} H, and / or A is preferably O, and / or n is preferably a number in the range from 2 to 4. As in the following As shown in formula (II), Z is preferably derived from an optionally substituted alkylbenzene unit in which a carbon atom of the aromatic ring is bonded to the unit C = A, and a carbon atom of the alkyl radical is bonded to the quaternary nitrogen atom and the methyl group is the preferred alkyl radical:

For the compounds of the formula (II), the definitions given for formula (I) for A, n, R ¹ to R ⁵ and R ⁸ , Y and X ^- likewise apply; R, R ⁶ and R ⁷ independently of one another represent H, a C ₁ -30 alkyl, C _3-30 cycloalkyl, aryl, alkylaryl or arylalkyl radical, one or more non-adjacent ones also not being present in these carbon atoms bonded to a heteroatom can be exchanged for a heteroatom, in particular N, O, S and / or Se. Preferably R, R ⁶ and / or R ^{7 are} H.

The invention also relates to the use of compounds of the general formula (I) for enhancing the cleaning performance of peroxygen-containing and, in particular, surfactant-containing detergents or cleaning agents in aqueous liquor.

The use according to the invention essentially consists in creating conditions under which the peroxygen compound and the compound of the general formula (I) can react with one another, with the aim of obtaining secondary products with a more strongly oxidizing effect. Such conditions exist in particular when the reactants meet in an aqueous system. This can be done by separately adding the peroxygen compound and the compound of the general formula (I) to a liquor which may optionally contain a detergent or cleaning agent. However, it is particularly advantageously carried out using a washing or cleaning agent which contains the compound of the formula (I) and a peroxidic oxidizing agent. The peroxygen compound can also be added separately, in bulk or as a preferably aqueous solution or suspension, to the aqueous system if a washing or cleaning agent free of peroxygen compounds is used. Depending on the intended use, the conditions can be varied widely. In addition to purely aqueous solutions, mixtures of water and suitable organic solvents can also be used as the reaction medium.

Further objects of the invention are a method for washing laundry and a method for cleaning hard surfaces, comprising the method _{steps (a) providing an aqueous liquor containing H 2} O ₂ or a particularly inorganic peroxygen compound which provides _{H 2} O _{2 in water and a} Compound according to general formula (I), and (b) bringing this liquor into contact with textiles to be washed or hard surfaces to be cleaned. The contact between the aqueous liquor and the object to be washed or cleaned is preferably established at temperatures in the range from 20.degree. C. to 40.degree. C., in particular from 20.degree. C. to 30.degree. The object to be washed or cleaned preferably remains in contact with the aqueous liquor for a period of from 20 minutes to 120 minutes, in particular from 30 minutes to 90 minutes. The methods according to the invention can be carried out manually or with the aid of conventional devices, for example washing machines or dishwashers. In the context of a use according to the invention and a method according to the invention, the amounts of peroxygen compounds used are generally chosen so that between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5000 ppm active oxygen, are present in the liquor.

A peroxygen compound together with a compound according to general formula (I) is preferably used for bleaching soiling, especially tea, when washing textiles, especially in an aqueous, surfactant-containing liquor. The phrase “bleaching of soiling” is to be understood in its broadest sense and includes both the bleaching of colored dirt on the textile, the bleaching of colored dirt in the wash liquor that has been detached from the textile and the oxidative destruction of itself the textile dyes in the wash liquor that detach from textiles under the washing conditions before they can be absorbed onto textiles of different colors.

Another preferred application form according to the invention is the use of a peroxygen compound together with the compound according to general formula (I) in, in particular, aqueous, surfactant-containing cleaning solutions for hard surfaces, in particular for dishes, for bleaching colored soiling, for example tea. Here, too, the term bleaching is understood to mean both the bleaching of dirt on the hard surface, in particular tea, and the bleaching of dirt that has been detached from the hard surface in the cleaning liquor, for example a dishwashing liquor.

The uses according to the invention for enhancing the cleaning performance of detergents and cleaning agents and for bleaching colored soiling can be realized particularly easily by introducing the compound of the general formula (I) into an aqueous liquor, in particular a surfactant-containing liquor, which also contains the peroxygen compound and that to be cleaned Textile or the object to be cleaned with a hard surface, the order in which the compound according to general formula (I), peroxygen compound and textile or object with a hard surface is introduced, or an in particular surfactant-containing aqueous liquor which contains the compound of the general formula ( I) and contains peroxygen compound, is applied to the textile to be cleaned or the hard surface to be cleaned. The compound of the general formula (I) is preferably used as a constituent of a washing or cleaning agent which particularly preferably also contains the peroxygen compound. The invention therefore furthermore relates to detergents or cleaning agents containing a compound according to general formula (I). A washing or cleaning agent preferably contains 0.01% by weight to 50% by weight, in particular 0.1% by weight to 25% by weight and particularly preferably 1% by weight to 10% by weight Compound according to general formula (I). The percentages by weight relate to the total detergent or cleaning agent; this also applies to all of the following percentages by weight, unless expressly stated otherwise. In aqueous washing or cleaning liquors, quantities of 1 g / l to 10 g / l, in particular 2 g / l to 5 g / l, of such agents are preferably used. The pH of the washing and cleaning liquors is generally not critical and can, for example, be in the range from pH 4 to pH 14; it is preferably in the range from pH 6 to pH 12, in particular from pH 7 to pH 10.

The above-mentioned preferred embodiments of the compounds of the formula (I) are also preferred for use in the processes, uses and compositions according to the invention.

The compounds of the formula (I) and the peracids formed from them under perhydrolysis conditions are generally more soluble in water than analogous compounds in which the cationic substituent is absent or which instead have an anionic substituent, and they have a higher affinity for the surface to be cleaned especially if it is made of cotton or contains cotton.

The detergents and cleaning agents according to the invention, which can be in particular powdery solids, in compacted particle form, as homogeneous solutions or as suspensions or dispersions, can in principle contain all known ingredients common in such agents in addition to the bleach-enhancing compound and preferably peroxygen compound used according to the invention. The detergents and cleaning agents according to the invention can in particular contain builder substances, surface-active surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, graying inhibitors, color transfer inhibitors, foam regulators, additional peroxygen activators and dyes and fragrances .

Suitable organic or inorganic peroxygen compounds are organic peracids or peracid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, but in particular inorganic peroxygen compounds such as hydrogen peroxide and inorganic salts which release hydrogen peroxide under the cleaning conditions, such as perborate, percarbonate and / or persilicate -Inclusion compounds, such as H ₂ O ₂ urea adducts, into consideration. Hydrogen peroxide can also be used with the help of an enzymatic system, that is, an oxidase and its substrate. If solid peroxygen compounds are to be used, these can be used in the form of powders or granules, which can also be coated in a manner known in principle. The peroxygen compounds can be added to the washing or cleaning liquor as such or in the form of agents containing them, which in principle can contain all customary detergent or cleaning agent constituents. Particular preference is given to using alkali percarbonate, alkali perborate monohydrate or hydrogen peroxide in the form of aqueous solutions which contain 3% by weight to 10% by weight hydrogen peroxide. Here and in the following, sodium is the preferred alkali metal. If a washing or cleaning agent according to the invention contains peroxygen compounds, in particular sodium percarbonate, these are preferably present in amounts from 1% by weight to 15% by weight, in particular from 4% by weight to 6% by weight.

As further compounds which provide peroxocarboxylic acid under perhydrolysis conditions, in particular compounds which, under perhydrolysis conditions, give optionally substituted perbenzoic acid and / or aliphatic peroxocarboxylic acids having 1 to 12 carbon atoms, in particular 2 to 4 carbon atoms, alone or in mixtures, can be used. The bleach activators cited at the outset which carry O- and / or N-acyl groups, in particular with the stated number of carbon atoms and / or optionally substituted benzoyl groups, are suitable. Polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated glycolurils, especially tetraacetylglycoluril (TAGU), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), N- are preferred Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates or carboxylates or the sulfonic or carboxylic acids of these, in particular nonanoyl or isononanoyl or lauroyloxybenzenesulfonate (NOBS or iso-NOBS or LOBS), 4- (2-oxycarbonyloxy) benzenesulfonate (DECOBS) or decanoyloxybenzoate (DOBA), acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran as well as acetylated sorbitol and mannitol and their mixtures (SORMAN), acylated sugar derivatives, especially pentaacetylglucose (PAG) , Pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose, acetylated, optionally N-alkylated glucamine and Eq uconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. A washing or cleaning agent according to the invention is preferably free from further compounds which produce peroxycarboxylic acid under perhydrolysis conditions.

in der R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_1-24-Alkyl- oder C₂-₂₄-Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN und -N⁽⁺⁾-CH₂-CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit mindestens einer, vorzugsweise zwei, gegebenenfalls substituierten C_1-24-Alkylgruppe(n) und gegebenenfalls weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃,-CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH2CH2-O)_nH mit n = 1, 2, 3, 4, 5 oder 6, R⁴ und R⁵ unabhängig voneinander eine voranstehend für R¹, R² oder R³ angegebene Bedeutung haben, wobei mindestens 2 der genannten Reste, insbesondere R² und R³, auch unter Einschluss des Stickstoffatoms und gegebenenfalls weiterer Heteroatome ringschließend miteinander verknüpft sein können und dann vorzugsweise einen Morpholino-Ring ausbilden, und X ein ladungsausgleichendes Anion, vorzugsweise ausgewählt aus Benzolsulfonat, Toluolsulfonat, Cumolsulfonat, den C_9-15-Alkylbenzolsulfonaten, den C_1-20-Alkylsulfaten, den C_8-22-Carbonsäuremethylestersulfonaten, Sulfat, Hydrogensulfat und deren Gemischen, ist, können eingesetzt werden.In addition to the other compounds mentioned which form peroxycarboxylic acids under perhydrolysis conditions, or instead of them, further bleach-activating compounds, such as, for example, nitriles, from which perimidic acids are formed, may be present. These include in particular aminoacetonitrile derivatives with a quaternized nitrogen atom according to the formula

in which R ¹ is -H, -CH _3, a C _2-24 -alkyl or -alkenyl radical, a substituted C _1-24 -alkyl or C _2-24 -alkenyl radical having at least one substituent from the group -Cl, -Br, -OH, -NH ₂ , -CN and -N ⁽⁺⁾ -CH ₂ -CN, an alkyl or alkenylaryl radical with a C _1-24 -alkyl group, or for a substituted alkyl or alkenylaryl radical with at least one, preferably two, optionally substituted C _1-24 -alkyl group (s) and optionally further substituents on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (CH2CH2-O) _n H with n = 1, 2, 3, 4, 5 or 6, R ⁴ and R ⁵ independently of one another have a ^{meaning given above for R 1} , R ² or R ³ , where at least 2 of the radicals mentioned, in particular R ² and R ³ , also including nitrogen ffatoms and optionally further heteroatoms can be linked to one another and then preferably form a morpholino ring, and X is a charge-balancing anion, preferably selected from benzenesulfonate, toluenesulfonate, cumene sulfonate, the C _9-15 alkylbenzenesulfonates, the C _1-20 alkyl sulfates, the C _8-22 -carboxylic acid methyl ester sulfonates, sulfate, hydrogen sulfate and mixtures thereof can be used.

The presence of bleach-catalyzing transition metal complexes is also possible. These are preferably selected from the cobalt, iron, copper, titanium, vanadium, manganese and ruthenium complexes. Both inorganic and organic compounds are suitable as ligands in the transition metal complexes, to which, in addition to carboxylates, in particular compounds with primary, secondary and / or tertiary amine and / or alcohol functions, such as pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, triazole, 2,2'-bispyridylamine, tris (2-pyridylmethyl) amine, 1,4,7 -Triazacyclononane, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,5,9-trimethyl-1,5,9-triazacyclododecane, (bis - ((1-methylimidazol-2-yl) methyl )) - (2-pyridylmethyl) -amine, N, N '- (bis- (1-methylimidazol-2-yl) -methyl) -ethylenediamine, N-bis- (2-benzimidazolylmethyl) -aminoethanol, 2,6- Bis- (bis- (2-benzimidazolylmethyl) aminomethyl) -4-methylphenol, N, N, N ', N'-tetrakis- (2-benzimidazolylmethyl) -2-hydroxy-1,3-diaminopropane, 2,6-bis - (bis- (2-pyridylmethyl) aminomethyl) -4-methylphenol, 1,3-bis- (bis- (2-benzimidazolylmethyl) aminomethyl) benzene, sorbitol, mannitol, erythritol, adonitol, inositol, lactose, and optionally substituted ones Salene, porphins, and porphyrins include. The inorganic neutral ligands include in particular ammonia and water. If not all coordination sites of the transition metal central atom are occupied by neutral ligands, the complex contains further, preferably anionic, and among these in particular monodentate or bidentate ligands. These include in particular the halides such as fluoride, chloride, bromide and iodide, and the (NO ₂ ) ^- group, that is to say a nitro ligand or a nitrito ligand. The (NO ₂ ) ^- group can also be bonded to a transition metal in a chelating manner, or it can bridge two transition metal atoms asymmetrically or η ¹ -O-. In addition to the ligands mentioned, the transition metal complexes to be used in the activator system according to the invention can also carry further ligands, as a rule more simply structured, in particular monovalent or polyvalent anion ligands. For example, nitrate, acetate, trifluoroacetate, formate, carbonate, citrate, perchlorate and complex anions such as hexafluorophosphate are possible. The anion ligands should ensure the charge balance between the transition metal central atom and the ligand system. The presence of oxo ligands, peroxo ligands and imino ligands is also possible. Such ligands in particular can also have a bridging effect, so that polynuclear complexes are formed. In the case of bridged, binuclear complexes, both metal atoms in the complex do not have to be the same. The use of binuclear complexes in which the two central transition metal atoms have different oxidation numbers is also possible. If anion ligands are absent or the presence of anion ligands does not lead to charge equalization in the complex, anionic counterions are present in the transition metal complex compounds, which neutralize the cationic transition metal complex. These anionic counterions include in particular nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate, perchlorate, the halides such as chloride or the anions of carboxylic acids such as formate, acetate, benzoate, citrate or oxalate. Examples of such additional transition metal _{complex compounds are Mn (IV) 2} (μ-0) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) -di-hexafluorophosphate, [N, N'-bis [( 2-hydroxy-5-vinylphenyl) methylene] -1,2-diaminocyclohexane] manganese (III) chloride, [N, N'-bis [(2-hydroxy-5-nitrophenyl) methylene] -1, 2-diaminocyclohexane] manganese (III) acetate, [N, N'-bis [(2-hydroxyphenyl) methylene] -1,2-phenylenediamine] manganese (III) acetate, [N, N ' -Bis [(2-hydroxyphenyl) methylene] -1,2-diaminocyclohexane] manganese (III) chloride, [N, N'-bis [(2-hydroxyphenyl) methylene] -1,2-diaminoethane] Manganese (III) chloride, [N, N'-bis [(2-hydroxy-5-sulfonatophenyl) methylene] -1,2-diaminoethane] manganese (III) chloride, manganese oxalate, nitropentammine cobalt (III) chloride, nitritopentammine cobalt (III) chloride, hexammine cobalt (III) chloride, chloropentammine cobalt (III) chloride and the peroxo complex [(NH ₃ ) ₅ Co-OO-Co (NH ₃ ) ₅ ] Cl ₄ .

The agents according to the invention can contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof. Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched alcohols each with 12 to 18 carbon atoms in the alkyl part and 3 to 20, preferably 4 to 10, alkyl ether groups. Corresponding ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to the long-chain alcohol derivatives mentioned in terms of the alkyl moiety, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical, can also be used.

Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations. Soaps that can be used are preferably the alkali metal salts of saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in a form that is not completely neutralized. The sulfate-type surfactants which can be used include the salts of the sulfuric acid half-esters of fatty alcohols with 12 to 18 carbon atoms and the sulfation products of the nonionic surfactants mentioned with a low degree of ethoxylation. The sulfonate-type surfactants that can be used include linear alkylbenzenesulfonates with 9 to 14 carbon atoms in the alkyl part, alkanesulfonates with 12 to 18 carbon atoms, and olefin sulfonates with 12 to 18 carbon atoms, which are formed when corresponding monoolefins are reacted with sulfur trioxide, as well as alpha-sulfo fatty acid esters, which are formed during the sulfonation of fatty acid methyl or ethyl esters.

Such surfactants are contained in the cleaning agents or detergents according to the invention in proportions of preferably 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight, during the agents according to the invention for cleaning hard surfaces, in particular dishes, contain preferably 0.1% by weight to 20% by weight, in particular 0.2% by weight to 5% by weight surfactants.

An agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid, sugar acids and carboxymethyl inulins, monomeric and polymeric aminopolycarboxylic acids, in particular glycine diacetic acid, methyl glycine diacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediaminoacetate, polyphylenediamine-N, n′-disuccinic acid ), Ethylenediaminetetrakis (methylenephosphonic acid), lysine tetra (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (polycarboxylic acids, in particular polycarboxylates accessible by oxidation of polysaccharides, polymeric acrylic polymers, maleic acids, methacrylic acids which can also contain small proportions of polymerizable substances without carboxylic acid functionality in polymerized form In the following: weight average) of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g / mol and 200,000 g / mol, those of the copolymers between 2,000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, each based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative average molecular weight of 50,000 g / mol to 100,000 g / mol. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid makes up at least 50% by weight. Terpolymers which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as a third monomer can also be used as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ carboxylic acid and preferably from a C ₃ -C ₄ monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ dicarboxylic acid, maleic acid being particularly preferred. In this case, the third monomeric unit is formed by vinyl alcohol and / or, preferably, an esterified vinyl alcohol. Vinyl alcohol derivatives which represent an ester of short-chain carboxylic acids, for example of C ₁ -C ₄ carboxylic acids, with vinyl alcohol are particularly preferred. Preferred polymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleate and 5% by weight to 40% by weight, preferably 10% by weight to 30% by weight, vinyl alcohol and / or vinyl acetate. Polymers in which the weight ratio of (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2, are very particularly preferred , 5: 1. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C ₁ -C ₄ -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives , is substituted. Preferred terpolymers contain 40% by weight to 60% by weight, in particular 45 to 55% by weight (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10% by weight to 30% by weight %, preferably 15% by weight to 25% by weight methallyl sulfonic acid or methallyl sulfonate and as the third monomer 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight of a carbohydrate. This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred. Sucrose is particularly preferred. The use of the third monomer presumably builds predetermined breaking points into the polymer, which are responsible for the good biodegradability of the polymer. These terpolymers generally have a relative average molecular weight between 1,000 g / mol and 200,000 g / mol, preferably between 200 g / mol and 50,000 g / mol. Further preferred copolymers are those which have acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers. The organic builder substances can, in particular for the production of liquid agents, be used in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali salts.

Such organic builder substances can, if desired, be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Quantities close to the upper limit mentioned are preferably used in paste-like or liquid, in particular water-containing, agents.

Particularly suitable water-soluble inorganic builder materials are polyphosphates, preferably sodium triphosphate. The water-insoluble inorganic builder materials used are in particular crystalline or amorphous, water-dispersible alkali metal alumosilicates, in amounts not exceeding 25% by weight, preferably from 3% by weight to 20% by weight and in particular in amounts from 5% by weight to 15% by weight. -% used. Among these, the crystalline sodium aluminosilicates in detergent quality, in particular zeolite A, zeolite P and zeolite MAP and optionally zeolite X, are preferred. Quantities close to the upper limit mentioned are preferably used in solid, particulate compositions. Suitable aluminosilicates in particular do not have any particles with a grain size greater than 30 μm and preferably consist of at least 80% by weight of particles with a size less than 10 μm. Their calcium binding capacity is usually in the range of 100 to 200 mg CaO per gram.

In addition or as an alternative to the mentioned water-insoluble aluminosilicate and alkali metal carbonate, further water-soluble inorganic builder materials can be contained. In addition to the polyphosphates such as sodium triphosphate, these include, in particular, the water-soluble crystalline and / or amorphous alkali silicate builders. Such water-soluble inorganic builder materials are contained in agents according to the invention preferably in amounts of from 1% by weight to 20% by weight, in particular from 5% by weight to 15% by weight. The alkali metal silicates which can be used as builder materials preferably have a molar ratio of alkali metal oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na ₂ O: SiO ₂ of 1: 2 to 1: 2.8. The crystalline silicates used alone or in a mixture with amorphous silicates are preferably crystalline sheet silicates of the general formula Na ₂ Si _x O _{2x + 1} y H ₂ O, in which x, the so-called module, is a number of 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline sheet silicates are those in which x in the general formula mentioned assumes the values 2 or 3. In particular, both β- and 5-sodium disilicates (Na ₂ Si ₂ O ₅ · y H ₂ O) are preferred. Virtually anhydrous crystalline alkali silicates of the above general formula, in which x is a number from 1.9 to 2.1, prepared from amorphous alkali silicates, can also be used in agents according to the invention. In a further preferred embodiment of agents according to the invention, a crystalline layered sodium silicate with a module of 2 to 3 is used, as can be produced from sand and soda. Sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further embodiment of the agents according to the invention. In a preferred embodiment of the agents according to the invention, a granular compound of alkali silicate and alkali carbonate is used, as is commercially available, for example, under the name Nabion® 15.

Machine dishwashing detergents according to the invention are preferably lower alkaline and contain the usual alkali carriers such as alkali metal silicates, alkali metal carbonates and / or alkali metal hydrogen carbonates. The alkali carriers commonly used include carbonates, hydrogen carbonates and alkali silicates with a molar ratio SiO ₂ / M ₂ O (M = alkali atom) of 1.5: 1 to 2.5: 1. %, based on the total agent, be included. The use of the highly alkaline metasilicates as alkali carriers is preferably not used at all. The alkali carrier system preferably used in the agents according to the invention is a mixture of carbonate and hydrogen carbonate, preferably sodium carbonate and hydrogen carbonate, which is contained in an amount of up to 60% by weight, preferably 10% by weight to 40% by weight . The ratio of carbonate used and hydrogen carbonate used varies depending on which pH value is ultimately desired, but usually an excess of sodium hydrogen carbonate is used, so that the weight ratio between hydrogen carbonate and carbonate is generally 1: 1 to 15: 1.

In a further embodiment of inventive agents for cleaning dishes, 20% by weight to 40% by weight of water-soluble organic builders, in particular alkali citrate, 5% by weight to 15% by weight alkali carbonate and 20% by weight to Contain 40% by weight alkali disilicate.

In particular, those from the class of proteases, lipases, cutinases, amylases, pullulanases, xylanases, hemicellulases, cellulases, peroxidases and oxidases or mixtures thereof come into consideration as enzymes optionally contained in the agents according to the invention, the use of protease, amylase, lipase and / or cellulase is particularly preferred. The proportion is preferably 0.2% by weight to 1.5% by weight, in particular 0.5% by weight to 1% by weight. The enzymes can be adsorbed on carrier substances in the usual way and / or embedded in coating substances or incorporated as concentrated liquid formulations which are as water-free as possible.

Suitable graying inhibitors or soil-release active ingredients are cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and mixed cellulose ethers, such as Methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose and methyl carboxymethyl cellulose. Sodium carboxymethyl cellulose and mixtures thereof with methyl cellulose are preferably used. The soil-release active ingredients usually used include copolyesters which contain dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. The proportion of graying inhibitors and / or soil release active ingredients in agents according to the invention is generally not more than 2% by weight and is preferably 0.5% by weight to 1.5% by weight.

For example, derivatives of diaminostilbene disulfonic acid or alkali metal salts thereof can be contained as optical brighteners for textiles made of cellulose fibers (for example cotton) in particular. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or similarly structured compounds are suitable instead of the morpholino group carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted 4,4'-distyryl-diphenyl type can be present, for example 4,4'-bis- (4-chloro-3-sulfostyryl) -diphenyl. Mixtures of brighteners can also be used. Brighteners of the 1,3-diaryl-2-pyrazoline type, for example 1- (p-sulfoamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline, and similarly structured compounds are particularly suitable for polyamide fibers. The content of optical brighteners or brightener mixtures in the agent is generally not more than 1% by weight, preferably 0.05% by weight to 0.5% by weight. In a preferred embodiment of the invention, the agent is free from such active ingredients.

The customary foam regulators that can be used in the agents according to the invention include, for example, polysiloxane-silica mixtures, the finely divided silica contained therein preferably being silanized or otherwise hydrophobized. The polysiloxanes can consist of both linear compounds and crosslinked polysiloxane resins and mixtures thereof. Further defoamers are paraffinic hydrocarbons, in particular microparaffins and paraffin waxes whose melting point is above 40 ° C, saturated fatty acids or soaps with in particular 20 to 22 carbon atoms, for example sodium behenate, and alkali salts of phosphoric acid mono- and / or dialkyl esters, in which the alkyl chains each have 12 to 22 carbon atoms. Among these, sodium monoalkyl phosphate and / or dialkyl phosphate having C ₁₆ to C ₁₈ alkyl groups is preferably used. The proportion of foam regulators can preferably be 0.2% by weight to 2% by weight.

The organic solvents that can be used in the agents according to the invention, especially when they are in liquid or pasty form, include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms , in particular ethylene glycol and propylene glycol, and mixtures thereof and the ethers which can be derived from the above-mentioned classes of compounds. Such water-miscible solvents are present in agents according to the invention in amounts of preferably not more than 20% by weight, in particular from 1% by weight to 15% by weight.

To set a desired pH value, which does not result from the mixture of the other components, the agents according to the invention can contain acids that are compatible with the system and the environment, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also contain mineral acids, in particular sulfuric acid or alkali hydrogen sulfates, or bases, in particular ammonium or alkali hydroxides. Such pH regulators are preferably contained in the agents according to the invention not more than 10% by weight, in particular from 0.5% by weight to 6% by weight.

The production of the solid compositions according to the invention presents no difficulties and can be carried out in a manner known in principle, for example by spray drying or granulation, the peroxygen compound and bleach catalyst optionally being added later separately.

Agents according to the invention in the form of aqueous solutions or solutions containing other customary solvents are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.

The agents according to the invention are preferably in the form of powdered, granular or tablet-shaped preparations, which can be prepared in a manner known per se, for example by mixing, granulating, roller compacting and / or by spray drying the thermally loadable components and admixing the more sensitive components, to which in particular enzymes, bleaches and Bleach-activating compounds can be expected. For the production of inventive agents with increased Bulk weight, in particular in the range from 650 g / l to 950 g / l, a method having an extrusion step is preferred.

To produce agents in tablet form, the preferred procedure is to mix all of the ingredients together in a mixer and then apply the mixture using conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the range from 200-10 ⁵ Pa to 1500 · 10 ⁵ Pa pressed. In this way, unbreakable tablets which dissolve sufficiently quickly under the conditions of use and have a flexural strength of normally more than 150 N are obtained without any problems mm to 40 mm.

The preparation of agents according to the invention in the form of non-dusting, storage-stable, free-flowing powders and / or granules with high bulk densities in the range from 800 g / l to 1000 g / l can also be carried out by mixing the builder components with at least one Proportion of liquid mixture components mixed with increasing the bulk density of this premix and subsequently - if desired after intermediate drying - the other components of the agent, including the performance-enhancing active ingredient or the performance-enhancing active ingredient combination, combined with the premix obtained in this way.

Examples

Example 1: Preparation of Bleach Enhancing Compounds

a): Preparation of 1-methyl-3- (4 - ((2-oxo-1,3-thiazolidin-3-yl) carbonyl) benzyl) -1H-imidazol-3-ium chloride

a) i): To a _{solution, heated to boiling under reflux under an N 2} atmosphere, of 41.3 g of 1,3, thiazolidin-2-one (200 mmol) and 60.7 g of triethylamine (1.5 equivalents) in 450 A solution of 75.6 g of 4-chloromethylbenzoyl chloride (400 mmol) in 50 ml of toluene was added dropwise to ml of toluene. The reaction mixture was taking Stirring heated to reflux for 6 hours, then allowed to cool to room temperature and filtered. The filtrate was stored in the refrigerator for 12 hours, the precipitate which had separated out was filtered off, _{washed with 5% strength aqueous NaHCO 3} solution and dried at 40 ° C. for 12 hours. 37.6 g (147 mmol; 51%) 3 - ((4- (chloromethyl) phenyl) carbonyl) -1,3-thiazolidin-2-one were obtained as a colorless solid.
FTIR (film): ṽ = 2949, 2892, 1703, 1670, 1611, 1357, 1290, 1224, 1153, 1018, 965, 848, 800, 765, 722, 671, 651, 479 cm ^-1 .
¹ H-NMR (400 MHz, CDCl ₃ ): δ = 3.39 (t, J = 7.0 Hz, 2H), 4.23 (t, J = 7.0 Hz, 2H), 4.60 ( s, 2H), 7.43 (pd, J = 8.1 Hz, 2H), 7.62 (pd, J = 8.5 Hz, 2H) ppm.
¹³ C-NMR (CDCl ₃ , 100.6 MHz): δ = 25.8 (t), 45.4 (t), 48.3 (t), 128.0 (d, 2C), 129.4 ( d, 2C), 133.5 (s), 141.5 (s), 169.1 (s), 172.3 (s).
a) ii): To a solution of 37.2 g of 3 - ((4- (chloromethyl) phenyl) carbonyl) -1,3-thiazolidin-2-one (145 mmol) prepared according to a) i) in 200 ml A solution of 23.8 g of 1-methylimidazole (290 mmol) in 20 ml of acetonitrile was added dropwise to acetonitrile under an N _{2 atmosphere and the reaction mixture was refluxed for 4 hours while stirring.} It was then cooled to room temperature and the solvent was removed on a rotary evaporator. 40 ml of acetone were added to the residue, the mixture was heated to 50-60 ° C. for 1 hour, then the acetone was removed by filtration and the process was repeated three times. Finally the residue was dried at 40 ° C. overnight. 37.2 g (110 mmol; 76%) 1-methyl-3- (4 - ((2-oxo-1,3-thiazolidin-3-yl) carbonyl) benzyl) -1 H-imidazole-3- ium chloride as a colorless solid.
FTIR (film): ṽ = 3149, 3006, 2944, 2852, 1779, 1697, 1668, 1306, 1284, 1228, 1156, 964, 844, 807, 735, 684, 624, 613, 470 cm ^-1 .
¹ H-NMR (400 MHz, D ₂ O): δ = 3.52 (t, J = 7.1 Hz, 2H), 3.97 (s, 3H), 4.27 (t, J = 7, 1 Hz, 2H), 5.51 (s, 2H), 7.52 (pd, J = 8.4 Hz, 2H), 7.55 (s, 2H), 7.70 (pd, J = 8, 4 Hz, 2H), 8.90 (s, 1H) ppm.
¹³ C-NMR (D ₂ O, 100.6 MHz): δ = 28.6 (t), 38.6 (q), 51.5 (t), 54.9 (t), 125.1 (d ), 126.7 (d), 131.0 (d, 2C), 132.1 (d, 2C), 136.9 (s), 139.8 (s), 140.7 (s), 173, 2 (s), 179.1 (s) ppm. MS (ESI positive mode, + 3.5 kV): 302 ([M-Cl ^- ] ⁺ , 100%).

Preparation of N, N, N-triethyl-N- (4 - ((2-oxo-1,3-oxazolidin-3-yl) carbonyl) benzyl) ethanaminium chloride

bi) To a N ₂ atmosphere to boiling under reflux heated solution of 51 g of 1,3-oxazolidine-2-one (590 mmol) and 81.8 ml of triethylamine (1.5 equivalents) in 600 ml of toluene was added a A solution of 112.6 g of 4-chloromethylbenzoyl chloride (600 mmol) in 100 ml of toluene was added dropwise. The reaction mixture was refluxed with stirring for 6 hours, then allowed to cool to room temperature and filtered. The filtrate was stored in the refrigerator for 12 hours, the precipitate which had separated out was filtered off, _{washed with 5% strength aqueous NaHCO 3} solution and dried at 40 ° C. for 12 hours. 44.7 g (186 mmol; 34%) 3 - ((4- (chloromethyl) phenyl) carbonyl) -1,3-oxazolidin-2-one were obtained as a colorless solid.
¹ H-NMR (400 MHz, CDCl ₃ ): δ = 4.04 (t, J = 9.4 Hz, 2H, CH ₂ ), 4.42-4.37 (m, 2H, CH ₂ ), 4 , 58 (s, 2H, CH ₂ ), 7.39-7.42 (m, 2H, Ar-H), 7.89-7.94 (m, 2H, Ar-H) ppm.
b) ii): To a solution of 50 g of 3 - ((4- (chloromethyl) phenyl) carbonyl) -1,3-oxazolidin-2-one (209 mmol) in 200 ml of acetonitrile, prepared according to b) i) a solution of 22.3 g of triethylamine (220 mmol) in 20 ml of acetonitrile was added dropwise under an N _{2 atmosphere and the reaction mixture was refluxed for 4 hours while stirring.} It was then cooled to room temperature and the solvent was removed on a rotary evaporator. 40 ml of acetone were added to the residue, the mixture was heated to 50-60 ° C. for 1 hour, then the acetone was removed by filtration and the process was repeated three times. Finally the residue was dried at 40 ° C. overnight. 35.8 g (105 mmol; 50%) of N, N, N-triethyl-N- (4 - ((2-oxo-1,3-oxazolidin-3-yl) carbonyl) benzyl) ethanaminium chloride were obtained as a colorless solid .
Melting point: 182-187 ° C FTIR (film): ṽ = 3053, 3025, 2985, 2949, 1779, 1672, 1455, 1391, 1361, 1339, 1232, 1196, 1180, 1104, 1031, 984, 921, 888, 848, 811, 755, 718, 669 cm ^-1 .
¹ H-NMR (400 MHz, D ₂ O / DMSO-d ₆ ): δ = 1.38 (t, J = 7.2 Hz, 9H, CH ₃ ), 3.26 (q, J = 7.1 Hz, 6H, CH ₂ ), 4.15 (t, J = 7.7 Hz, 2H, CH ₂ ), 4.55 (t, J = 7.7 Hz, 2H, CH ₂ ), 4.57 ( s, 2H, CH _2), 7.68 (pd, J = 8.4 Hz, 2H, Ar-H), 7.80 (pd, J = 8.4 Hz, 2H, Ar-H) ppm.
¹³ C-NMR (D ₂ O / DMSO-d ₆ , 100.6 MHz): δ = 7.9 (q, 3C), 43.8 (t), 52.8 (t, 3C), 59.6 (t), 63.3 (t), 129.3 (d, 2C), 131.2 (s), 132.4 (d, 2C), 135.7 (s), 153.9 (s), 169.1 (s). MS (ESI positive mode, + 4.5 kV): 305 ([M-Cl ^- ] ⁺ , 100%).

Preparation of 1- (4 - ((2-Oxo-1,3-oxazolidin-3-yl) carbonyl) benzyl) pyridinium chloride

A solution of 50 g of 3 - ((4- (chloromethyl) phenyl) carbonyl) -1,3-oxazolidin-2-one (209 mmol) in 200 ml of acetonitrile was added under an N ₂ atmosphere a solution of 17.4 g of pyridine (220 mmol) in 20 ml of acetonitrile was added dropwise and the reaction mixture was refluxed for 4 hours while stirring. It was then cooled to room temperature and the solvent was removed on a rotary evaporator. 40 ml of acetone were added to the residue, the mixture was heated to 50-60 ° C. for 1 hour, then the acetone was removed by filtration and the process was repeated three times. Finally the residue was dried at 40 ° C. overnight. 32 g (100 mmol; 48%) 1- (4 - ((2-oxo-1,3-oxazolidin-3-yl) carbonyl) benzyl) pyridinium chloride were obtained as a beige solid.
Melting point: 97-111 ° C.
FTIR (film): ṽ = 3133, 3094, 3032, 2991, 2953, 2877, 1762, 1673, 1633, 1495, 1377, 1328, 1216, 1100, 1037, 996, 918, 811, 751, 729, 709, 687 , 591, 454 cm ^-1 .
¹ H-NMR (400 MHz, D ₂ O / DMSO-d ₆ ): δ = 4.09 (t, J = 7.7 Hz, 2H, CH ₂ ), 4.49 (t, J = 7.7 Hz, 2H, CH _2), 6.09 (s, 2H, CH _2), 7.64 to 7.73 (m, 4H, Ar-H), 8.21 to 8.28 (m, 2H, Ar -H), 8.66-8.72 (m, 1H, Ar-H), 9.42-9.46 (m, 2H, Ar-H), ppm.
¹³ C-NMR (D ₂ O / DMSO-d ₆ , 100.6 MHz): δ = 43.4 (t), 62.6 (t), 62.8 (t), 128.1 (d, 2C ), 128.6 (d, 2C), 129.3 (d, 2C), 134.5 (s), 137.4 (s), 145.1 (d, 2C), 146.2 (d), 153.3 (s), 168.5 (s). MS (ESI positive mode, + 4.5 kV): 283 ([M-Cl ^- ] ⁺ , 100%).

Preparation of 3-methyl-1- (4 - ((2-oxo-1,3-oxazolidin-3-yl) carbonyl) benzyl) pyridinium chloride

A solution of 50 g of 3 - ((4- (chloromethyl) phenyl) carbonyl) -1,3-oxazolidin-2-one (209 mmol) in 200 ml of acetonitrile was added under an N ₂ atmosphere a solution of 20.5 g of 3-methylpyridine (220 mmol) in 200 ml of acetonitrile was added dropwise and the reaction mixture was refluxed for 4 hours while stirring. It was then cooled to room temperature and the solvent was removed on a rotary evaporator. 40 ml of acetone were added to the residue, the mixture was heated to 50-60 ° C. for 1 hour, then the acetone was removed by filtration and the process was repeated three times. Finally the residue was dried at 40 ° C. overnight. 40 g (120 mmol; 57%) of 3-methyl-1- (4 - ((2-oxo-1,3-oxazolidin-3-yl) carbonyl) benzyl) pyridinium chloride were obtained as a light beige solid.
Melting point: 108-113 ° C FTIR (film): ṽ = 3026, 2988, 2910, 1766, 1675, 1377, 1322, 1216, 1143, 1098, 1032, 988, 915, 870, 827, 805, 761, 730, 709, 689, 650, 633, 597 cm ^-1 .
¹ H-NMR (400 MHz, D ₂ O / DMSO-d ₆ ): δ = 2.59 (s, 3H, CH ₃ ), 4.13 (t, J = 7.7 Hz, 2H, CH ₂ ) , 4.54 (t, J = 7.7 Hz, 2H, CH ₂ ), 6.00 (s, 2H, CH ₂ ), 7.68-7.77 (m, 4H, Ar-H), 8.14 (dd, J = 6.1 Hz, 8.0 Hz, 1H, Ar-H), 8.54 (d, J = 8.0 Hz, 1H, Ar-H), 9.18 (d, J = 6.1 Hz, 1H, Ar-H), 9.29 (s, 1H, Ar-H) ppm. ¹³ C-NMR (D ₂ O / DMSO-d ₆ , 100.6 MHz): δ = 18.3 (q), 43.7 (t), 63.0 (t), 63.1 (t), 128.2 (d), 128.4 (d, 2C), 129.7 (d, 2C), 134.8 (s), 137.5 (s), 140.0 (s), 142.4 ( d), 144.6 (d), 146.9 (d), 153.7 (s), 169.0 (s).
MS (ESI positive mode, + 4.5 kV): 297 ([M-Cl ^- ] ⁺ , 100%).

Preparation of 3-methyl-1- (4 - ((2-oxo-1,3-thiazolidin-3-yl) carbonyl) benzyl) pyridinium chloride

A solution of 30 g of 3 - ((4- (chloromethyl) phenyl) carbonyl) -1,3-thiazolidin-2-one (117 mmol) in 150 ml of acetonitrile was added under an N ₂ atmosphere a solution of 11.5 g of 3-methypyridine (123 mmol) in 25 ml of acetonitrile was added dropwise and the reaction mixture was refluxed for 4 hours while stirring. It was then cooled to room temperature and the solvent was removed on a rotary evaporator. To the residue was added 40 ml of acetone, the mixture was heated to 50-60 ° C for 1 hour, then the acetone was removed by filtration, and the process was repeated three times. Finally the residue was dried at 40 ° C. overnight. 19.5 g (55.8 mmol; 48%) 3-methyl-1- (4 - ((2-oxo-1,3-thiazolidin-3-yl) carbonyl) benzyl) pyridinium chloride were obtained as a yellow, hygroscopic solid .
FTIR (film): ṽ = 3050, 3007, 2910, 1697, 1665, 1507, 1441, 1310, 1289, 1278, 1247, 1155, 1019, 960, 850, 806, 737, 698, 671, 655, 643, 629 , 465 cm ^-1 .
¹ H-NMR (400 MHz, MeOD-d ₃ / CDCl ₃ ): δ = 2.61 (s, 3H), 3.47 (t, J = 7.1 Hz, 2H), 4.27 (t, J = 7.1 Hz, 2H), 5.93 (s, 2H), 7.53 (pd, J = 8.6 Hz, 2H), 7.66 (pd, J = 8.4 Hz, 2H) , 7.98 (dd, J = 6.2 Hz, 7.9 Hz, 1H), 8.32 (d, J = 8.0 Hz, 1H), 9.05 (d, J = 6.1 Hz , 1H), 9.03 (s, 1H) ppm.
¹³ C-NMR (CDCl3, 100.6 MHz): δ = 19.2 (q), 26.2 (t), 48.9 (t), 63.0 (t), 128.0 (d), 129.7 (d, 2C), 129.9 (d, 2C), 135.5 (s), 137.5 (s), 140.2 (s), 142.9 (d), 145.3 ( d), 146.5 (d), 169.4 (s), 173.1 (s). MS (ESI positive mode, + 3.5 kV): 252 (14%), 284 (24%), 313 ([M-Cl ^- ] ⁺ , 100%).

Example 2: Discoloration attempt

To a solution, adjusted to pH 10-11 by adding NaOH, of 2.5 mg of morin in 100 ml of water, 98 mg of sodium percarbonate and 13.1 mg of TAED or one of the compounds described in Examples 1 a), b), c), d) and e) were prepared, added and stirred at room temperature. The time taken for the yellow color to completely disappear was determined and is shown in Table 1. Table 1: Time to complete discoloration Active ingredient Duration [minutes] TAED 210 Compound from example 1 a) 270 Compound from example 1 b) 110 Compound from example 1 c) 120 Connection from example 1 d) 115 Connection from example 1 e) 125

Example 3: washing trials

Washing tests were carried out at 30 ° C. with standardized soiling on cotton specified in Table 3, using a washing liquor with 3.8 g / l each of a solid detergent of the composition specified in Table 2 below, the agents M1, M2, M3, M4 and M5 the compounds according to the invention prepared in Example 1 b), c), d), e) and f), and for comparison the agent V1 did not contain such a compound but rather the conventional bleach activator TAED. The evaluation was carried out by measuring the color distance according to the L * a * b * values and the Y values calculated therefrom as a measure of the brightness. Table 3 shows the differences in the Y values that resulted after washing between V1 and M1, V1 and M2, V1 and M3, V1 and M4 and V1 and M5. Table 2: Composition (% by weight) V1 M1 M2 M3 M4 M5 Na-alkylbenzenesulfonate 13th 13th 13th 13th 13th 13th Na fatty alcohol sulfate 3 3 3 3 3 3 Na carboxymethyl cellulose 3 3 3 3 3 3 HEDP-Na4 1 1 1 1 1 1 Na polyacrylate 3 3 3 3 3 3 Sodium silicate 7th 7th 7th 7th 7th 7th sodium 21 21 21 21 21 21 Sodium bicarbonate 10 10 10 10 10 10 Sodium percarbonate 12th 12th 12th 12th 12th 12th TAED 3.1 - - - - - Compound from example 1 b) - 3.1 - - - - Compound from example 1 c) - - 3.1 - - - Connection from example 1 d) - - - 3.1 - - Connection from example 1 e) - - - - 3.1 - Connection from example 1 f) - - - - - 3.1 Sodium sulfate, water, perfume, dye to 100 Table 3: ΔY values Soiling / medium M1 M2 M3 M4 M5 red wine 5.9 4.1 2.8 4.7 5.3 coffee 4.0 3.6 1.7 4.2 5.0 Beetroot 2.8 3.0 3.3 4.9 6.0 Blackcurrant 1.2 2.1 0.9 3.3 3.4 tea nb 1.5 1.6 1.6 2.0 nb: not determined

The brightness values when the active ingredients essential to the invention are used are greater than those which result when the detergent containing another bleach activator is used.

Example 4: cleaning attempts

0.5 g of a mixture of lactose and ovalbumin (weight ratio 3: 1) was stirred in 10 ml of water at room temperature for 10 minutes, then the mixture was freeze-dried, ground in a mortar and heated to 160 ° C for 20 minutes. Mixtures of 15 mg each of the burnt-on food residue-simulating soil obtained in this way, 3.75 mg of sodium percarbonate and 0.5 mg of a compound prepared in Example 1 b), c), d) or e) in 5 ml of water were for 48 hours in heated to 60 ° C using a mechanical shaker. After the periods of time indicated in Table 4, the dissolution of the artificial dirt was visually evaluated and rated on a scale from 0 (no dissolution) to ++++ (completely dissolved). Table 4: Dissolution of burnt-on dirt Active ingredient / duration 0.5h 1h 2h 4h 6h 24 hours 48h no 0 0 0 0 0 0 0 Compound from example 1 b) + + ++ +++ +++ +++ ++++ Compound from example 1 c) 0 0 + + + + + Connection from example 1 d) + + + + + + ++ Connection from example 1 e) 0 0 + + + + +

QUOTES INCLUDED IN THE DESCRIPTION

This list of the documents listed by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent literature cited

• WO 96/06915 A1 [0005]

Claims (10)

Bleach-activating compound of the general formula (I),

in the A for O, S, Se; Z represents an optionally substituted C _1-30 alkylene, C _3-30 cycloalkylene, arylene, alkylenearylene or arylenealkylene radical; X ^- for an anion, in particular chloride, bromide, iodide, tosylate, mesylate, triflate, sulfate, carbonate and / or phosphate; ^{Y is} NR ^8, O, S, Se, C (R ⁸ ) ₂ ; R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁸ independently of one another represent H, a C _1-30 alkyl, C _3-30 cycloalkyl, aryl, alkylaryl or arylalkyl radical, where two or several of the radicals R ³ , R ⁴ and R ^{5 can} also be connected to one another and form a stated cycloalkyl or aryl radical; and n stands for a number in the range from 1 to 12, it being possible for 1 or more non-adjacent carbon atoms not bonded to a heteroatom in the hydrocarbon radicals to be replaced by a heteroatom, in particular N, O, S and / or Se. Use of compounds of the general formula (I),

in the A for O, S, Se; Z represents an optionally substituted C _1-30 alkylene, C _3-30 cycloalkylene, arylene, alkylenearylene or arylenealkylene radical; X ^- for an anion, in particular chloride, bromide, iodide, tosylate, mesylate, triflate, sulfate, carbonate and / or phosphate; Y is NR ^8, O, S, Se, C (R ⁸ ) ₂ ; R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁸ independently of one another represent H, a C _1-30 alkyl, C _3-30 cycloalkyl, aryl, alkylaryl or arylalkyl radical, where two or several of the radicals R ³ , R ⁴ and R ^{5 can} also be connected to one another and form a stated cycloalkyl or aryl radical; and n stands for a number in the range from 1 to 12, where in the hydrocarbon radicals 1 or more non-adjacent carbon atoms not bonded to a heteroatom can be replaced by a heteroatom, in particular N, O, S and / or Se, to increase the cleaning performance of peroxygen-containing and especially surfactant-containing detergents or cleaning agents in aqueous liquor. Use after Claim 2 , characterized in that the compound of general formula (I) is introduced into a particularly surfactant-containing aqueous liquor which also contains peroxygen compound and the textile to be cleaned or the object to be cleaned with a hard surface, the sequence of introduction of the compound according to the general formula (I), peroxygen compound and textile or object with a hard surface is arbitrary, or an in particular surfactant-containing aqueous liquor which contains the compound of the general formula (I) and peroxygen compound is applied to the textile to be cleaned or the hard surface to be cleaned. A process for washing laundry or a process for cleaning hard surfaces, comprising the process _{steps (a) providing an aqueous liquor containing H 2} O ₂ or a _{particularly inorganic peroxygen compound which provides H 2} O ₂ in water and a compound according to general formula (I) ,

in the A for O, S, Se; Z represents an optionally substituted C _1-30 alkylene, C _3-30 cycloalkylene, arylene, alkylenearylene or arylenealkylene radical; X ^- for an anion, in particular chloride, bromide, iodide, tosylate, mesylate, triflate, sulfate, carbonate and / or phosphate; Y is NR ^8, O, S, Se, C (R ⁸ ) ₂ ; R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁸ independently of one another represent H, a C _1-30 alkyl, C _3-30 cycloalkyl, aryl, alkylaryl or arylalkyl radical, where two or several of the radicals R ³ , R ⁴ and R ^{5 can} also be connected to one another and form a stated cycloalkyl or aryl radical; and n stands for a number in the range from 1 to 12, where in the hydrocarbon radicals 1 or more non-adjacent carbon atoms not bonded to a heteroatom can be replaced by a heteroatom, in particular N, O, S and / or Se, and (b) bringing this liquor into contact with fabrics to be washed or hard surfaces to be cleaned. Procedure according to Claim 4 , characterized in that the contact between the aqueous liquor and the object to be washed or cleaned is established at temperatures in the range from 20 ° C to 40 ° C, in particular from 20 ° C to 30 ° C. Procedure according to Claim 4 or 5 , characterized in that the object to be washed or cleaned remains in contact with the aqueous liquor for a period of 20 minutes to 120 minutes, in particular from 30 minutes to 90 minutes. Use after Claim 2 or 3 or method according to one of the Claims 4 to 6th , characterized in that the amounts of peroxygen compounds used are chosen so that between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5000 ppm active oxygen, are present in the liquor. Washing or cleaning agents containing a compound according to general formula (I),

in the A for O, S, Se; Z represents an optionally substituted C _1-30 alkylene, C _3-30 cycloalkylene, arylene, alkylenearylene or arylenealkylene radical; X- for an anion, in particular chloride, bromide, iodide, tosylate, mesylate, triflate, sulfate, carbonate and / or phosphate; Y for NR ^8, O, S, Se; R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁸ independently of one another represent H, a C _1-30 alkyl, C _3-30 cycloalkyl, aryl, alkylaryl or arylalkyl radical, where two or several of the radicals R ³ , R ⁴ and R ^{5 can} also be connected to one another and form a stated cycloalkyl or aryl radical; and n stands for a number in the range from 1 to 12, it being possible for 1 or more non-adjacent carbon atoms not bonded to a heteroatom in the hydrocarbon radicals to be replaced by a heteroatom, in particular N, O, S and / or Se. Means after Claim 7 , characterized in that it contains 0.01% by weight to 50% by weight, in particular 0.1% by weight to 25% by weight, of the compound according to general formula (I). Use, means or method according to one of the preceding claims, characterized in that the compound of the general formula (I) corresponds to the general formula (II),

in which R, R ⁶ and R ^7, independently of one another, represent H, a C _1-30 alkyl, C _3-30 cycloalkyl, aryl, alkylaryl or arylalkyl radical, in which one or more non-adjacent ones are not carbon atoms bonded to a heteroatom can be exchanged for a heteroatom, in particular N, O, S and / or Se.