DE102015225880A1 - Pyridine group-containing acylhydrazones - Google Patents

Abstract

The cleaning performance of detergents and cleaning agents against soiling should be improved. This was achieved mainly by incorporating pyridine group-containing acylhydrazones.

Description

The present invention relates to certain acylhydrazones and their use for the removal of soils from textile or hard surfaces, optionally in combination with oxygenated bleaches or reducing agents, as well as detergents and cleaners containing such acylhydrazones.

Conventional detergents with bleaching agents based on active oxygen, especially in the presence of conventional stoichiometric activators (such as TAED, NOBS, DECOBS, DOBA) show good performance at use temperatures of 40 ° C and above. At lower temperatures, however, their performance is sometimes perceived as in need of improvement. Thus, at wash temperatures below 40 ° C., not all bleachable or non-bleachable soiling can always be sufficiently removed. Consumers tend to wash at ever lower temperatures, but still expect a satisfactory performance from their detergent. High washing temperatures are also associated with increased energy consumption, which is to be avoided due to environmental protection and resource conservation.

From the international patent application WO 2009/124855 For example, metal complexes with acylhydrazone ligands bearing electron-withdrawing substituents near the acyl group are known. The international patent application WO 2012/080088 discloses acylhydrazones having cyclic ammonium groups as substituents in the vicinity of the acyl group.

It has now been found that certain pyridine-group-containing acylhydrazones have a particularly pronounced bleach-enhancing effect, especially at low temperatures.

in der R¹ für eine CF₃ oder für eine gegebenenfalls substituierte C_1-28-Alkyl-, C_2-28-Alkenyl-, C_2-22-Alkinyl-, C_3-12-Cycloalkyl-, C_3-12-Cycloalkenyl-, Phenyl-, Naphthyl-, C_7-9-Aralkyl, C_3-20-Heteroalkyl- oder C_3-12-Cycloheteroalkylgruppe,
einer der Reste R² und R³ für eine gegebenenfalls substituierte Pyridingruppe und der andere der Reste R² und R³ für Wasserstoff oder eine gegebenenfalls substituierte C_1-28-Alkyl-, C_2-28-Alkenyl-, C_2-22-Alkinyl-, C_3-12-Cycloalkyl-, C_3-12-Cycloalkenyl-, C_7-9-Aralkyl-, C_3-28-Heteroalkyl-, C_3-12-Cycloheteroalkyl-, C_5-16-Heteroaralkyl-, Phenyl-, Naphthyl- oder Heteroarylgruppe, und
R⁴ für Wasserstoff oder eine C_1-28-Alkyl-, C_2-28-Alkenyl-, C_2-22-Alkinyl-, C_3-12-Cycloalkyl-, C_3-12-Cycloalkenyl-, C_7-9-Aralkyl-, C_3-20-Heteroalkyl-, C_3-12-Cycloheteroalkyl-, C_5-16-Heteroaralkylgruppe oder eine gegebenenfalls substituierte Phenyl- oder Naphthyl- oder Heteroarylgruppe stehen. An object of the present invention are acylhydrazones of general formula I,

in the R ^{1 is} a CF ₃ or an optionally substituted C _1-28 alkyl, C _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 Cycloalkenyl, phenyl, naphthyl, C _7-9 -aralkyl, C _3-20 -heteroalkyl or C _3-12 -cycloheteroalkyl group,
one of the radicals R ² and R ^{3 is} an optionally substituted pyridine group and the other of the radicals R ² and R ^{3 is} hydrogen or an optionally substituted C _1-28 alkyl, C _2-28 alkenyl, C _2-22 Alkynyl, C _3-12 -cycloalkyl, C _3-12 -cycloalkenyl, C _7-9 -aralkyl, C _3-28 -heteroalkyl, C _3-12 -cycloheteroalkyl, C _5-16 -heteroaralkyl- , Phenyl, naphthyl or heteroaryl group, and
R ^{4 is} hydrogen or a C _1-28 alkyl, C _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 cycloalkenyl, C _7-9 -Aralkyl, C _3-20 heteroalkyl, C _3-12 cycloheteroalkyl, C _5-16 heteroaralkyl or an optionally substituted phenyl or naphthyl or heteroaryl group.

The pyridine group-containing acylhdrazones enhance the bleaching effect of common peroxygen bleaches. Further objects of the invention are therefore the use of a combination of a peroxidic bleach with such an acylhydrazone to improve the soil removal performance of detergents in their use, the use of such an acylhydrazone to improve the bleaching performance of peroxidic bleach in detergents or cleaners in their use Application, and a method for removing stains from textile or hard surfaces by contacting the stained surface with an aqueous preparation containing peroxidic bleach and such acylhydrazone.

It has been observed that the abovementioned acylhydrazones, even in the absence of peroxidic bleaches, improve the soil removal performance of detergents and cleaners, in particular with respect to bleachable or enzyme-sensitive stains. Further objects of the invention are therefore the use of a cited acylhydrazone for improving the soil removal performance of detergents or cleaning agents in their use, and a process for removing stains from textile or hard surfaces by bringing the contaminated surface into contact with an aqueous preparation, containing such acylhydrazone. The improvement in performance of the peroxidic bleach-free detergents and cleaning agents is particularly pronounced in the simultaneous presence of a Reducing agent, so that these variants of the above-described subjects of the invention are further preferred articles of the invention.

Another object of the invention is a washing or cleaning agent containing a named acylhydrazone. This contains in a preferred embodiment of the invention peroxide bleaching agent, and in another preferred embodiment of the invention reducing agent and is then preferably free of bleaching agents.

A reducing agent is a substance that releases electrons, thus reducing other substances and thereby oxidizing itself. By its presence, the oxidation of other detergent ingredients and the associated decrease in performance during storage of the agent is prevented or at least reduced. However, the improvement of the soil removal performance of liquid agents achieved by the combination according to the invention is also observed in freshly prepared acylhydrazone and reducing agent-containing agents. Preferred reducing agents are selected from hydroxylamine, which can be used as such or in the form of an acid addition compound, for example hydrochloride, ascorbic acid, ascorbic acid alkali metal salts, isoascorbic acid, isoascorbic acid alkali metal salts, alkali metal sulfites, alkali hydrogen sulfites, aldehydes such as hydroxypropanedial, and mixtures of two or more of these. If reducing agent is present, the weight ratio of acylhydrazone to reducing agent is preferably in the range from 5: 1 to 1: 5000, in particular from 4: 1 to 1:40. Inventive compositions or agents used in the context of a use according to the invention or a process according to the invention preferably contain from 0.1% by weight to 5% by weight, in particular from 0.5% by weight to 2% by weight, of reducing agent.

By the use according to the invention of the acylhydrazone in the process according to the invention and when using an agent according to the invention, in particular the removal of bleachable stains is improved, which is particularly notable in the absence of the presence of bleaching agents. Likewise, the removal of enzyme-sensitive stains is improved.

Bleachable stains are to be understood as meaning those which are colored and, after washing in the presence of a peroxidic bleaching agent, such as, for example, sodium percarbonate, and optionally a bleach activator, such as N, N, N ', N'-tetraacetylethylenediamine, are removed more strongly or at least have a lighter shade than after washing without the peroxidic bleach and optionally the bleach activator. The bleachable stains usually contain polymerizable substances, in particular dyes, wherein the dyes are preferably polyphenolic dyes, in particular flavonoids, especially anthocyanidins or anthocyanins or oligomers of these compounds. In addition to removing stains in the colors green, yellow, red or blue, stains in intermediate colors, in particular violet, purple, brown, purple or pink, as well as stains, which are green, yellow, red and violet, come into consideration Purple, brown, purple, pink or blue tint, without essentially being made entirely of this color itself. The colors mentioned can also be light or dark in each case. These are preferably stains, in particular stains of grass, fruits or vegetables, in particular soiling by food products, such as spices, sauces, chutneys, curries, purees and jams, or drinks, such as coffee, tea, wines and Juices containing the corresponding green, yellow, red, purple, purple, brown, purple, pink and / or blue dyes.

By enzyme-sensitive soils are meant those which are more strongly removed after washing in the presence of enzymes or, if they are colored, have a lighter shade than after washing without the enzyme. Preferably, it is proteinaceous, polysaccharide-containing and / or fatty soils, such as egg, blood, starch, mannan, grass, or sauces.

The acylhydrazones may be in E or Z configuration; when R ^{2 is} hydrogen, the compound of general formula (I) may be in one of its tautomeric forms or as a mixture of these.

In the compounds of general formula (I), R ^{2 is} preferably hydrogen. R ¹ and / or R ³ is preferably an electron-withdrawing group-substituted methyl, phenyl or naphthyl group. R ⁴ is preferably hydrogen. As an electron-withdrawing group is preferably an ammonium group in question, which optionally carries alkyl or hydroxyalkyl groups or is formed with the inclusion of the N-atom carrying an alkyl group as heterocycloalkyl optionally carrying further heteroatoms.

in der R¹ für eine C_1-4-Alkylgruppe, die einen Substituenten

trägt, in dem R¹⁰ für Wasserstoff oder eine C_1-28-Alkyl-, C_2-28-Alkenyl-, C_2-22-Alkinyl-, C_3-12-Cycloalkyl-, C_3-12-Cycloalkenyl-, C_7-9-Aralkyl-, C_3-20-Heteroalkyl-, C_3-12-Cycloheteroalkyl-, C_5-16-Heteroaralkylgruppe und A^– für das Anion einer organischen oder anorganischen Säure steht, R² und R⁴ die für Formel (I) angegebene Bedeutung haben und
R⁵, R⁶, R⁷ und R⁸ unabhängig voneinander für R¹, Wasserstoff, Halogen, eine Hydroxy-, Amino-, eine gegebenenfalls substituierte N-mono-oder di-C_1-4-alkyl- oder C_2-4-hydroxyalkyl-amino-, N-Phenyl- oder N-Naphthyl-amino-, C_1-28-Alkyl-, C_1-28-Alkoxy-, Phenoxy-, C_2-28-Alkenyl-, C_2-22-Alkinyl-, C_3-12-Cycloalkyl-, C_3-12-Cycloalkenyl-, C_7-9-Aralkyl-, C_3-20-Heteroalkyl-, C_3-12-Cycloheteroalkyl-, C_5-16-Heteroaralkyl-, Phenyl- oder Naphthylgruppe stehen, wobei die Substituenten ausgewählt werden aus C_1-4-Alkyl-, C_1-4-Alkoxy-, Hydroxy-, Sulfo-, Sulfato-, Halogen-, Cyano-, Nitro-, Carboxy-, Phenyl-, Phenoxy-, Naphthoxy-, Amino-, N-mono-oder di-C_1-4-alkyl- oder C_2-4-hydroxyalkyl-amino-, N-Phenyl- oder N-Naphthyl-aminogruppen, oder
R⁵ und R⁶ oder R⁶ und R⁷ oder R⁷ und R⁸ unter Ausbildung von 1, 2 oder 3 carbocyclischen oder O-, NR¹⁰- oder S-heterocyclischen, gegebenenfalls aromatischen und/oder gegebenenfalls C_1-6-alkylsubstituierten Ringen miteinander verbunden sind. Preferred embodiments of the acylhydrazones include those of the general formula (II),

in the R ^{1 is} a C _1-4 alkyl group having a substituent

in which R ^{10 represents} hydrogen or a C _1-28 -alkyl, C _2-28 -alkenyl, C _2-22 -alkynyl, C _3-12 -cycloalkyl, C _3-12 -cycloalkenyl-, C _7-9 aralkyl, C _3-20 heteroalkyl, C _3-12 cycloheteroalkyl, C _5-16 heteroaralkyl, and A ^{- represents} the anion of an organic or inorganic acid; R ² and R ^{4 represent} the Have the meaning given in formula (I) and
R ⁵ , R ⁶ , R ⁷ and R ⁸ independently of one another are R ¹ , hydrogen, halogen, a hydroxy, amino, an optionally substituted N-mono or di-C _1-4 -alkyl or C _2-4 -hydroxyalkylamino, N-phenyl or N-naphthylamino, C _1-28 alkyl, C _1-28 alkoxy, phenoxy, C _2-28 alkenyl, C _2-22 Alkynyl, C _3-12 cycloalkyl, C _3-12 cycloalkenyl, C _7-9 aralkyl, C _3-20 heteroalkyl, C _3-12 cycloheteroalkyl, C _5-16 heteroaralkyl , Phenyl or naphthyl group, wherein the substituents are selected from C _1-4 alkyl, C _1-4 alkoxy, hydroxy, sulfo, sulfato, halogen, cyano, nitro, carboxy, Phenyl, phenoxy, naphthoxy, amino, N-mono or di-C _1-4 alkyl or C _2-4 hydroxyalkylamino, N-phenyl or N-naphthylamino groups, or
R ⁵ and R ⁶ or R ⁶ and R ⁷ or R ⁷ and R ⁸ to form 1, 2 or 3 carbocyclic or O, NR ¹⁰ - or S-heterocyclic, optionally aromatic and / or optionally C _1-6 alkyl substituted Rings are interconnected.

Particularly preferred is the presence of the substituent

The anion A ^- is preferably carboxylate such as lactate, citrate, tartrate or succinate, perchlorate, tetrafluoroborate, hexafluorophosphate, alkyl sulfonate, alkyl sulfate, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, isocyanate, rhodanide, nitrate, fluoride, chloride, bromide, bicarbonate or Carbonate, wherein in polyvalent anions, the charge balance can be achieved by correspondingly more cationic acylhydrazones or optionally by the presence of additional cations such as sodium or ammonium ions.

Particularly preferred is the acylhydrazone of the formula

Acylhydrazones which are essential to the invention can be prepared in a manner known in principle by reacting carboxylic acid hydrazides with carbonyl-substituted pyridine compounds at position 2.

The agents may be hard surface cleaners such as dishes, floor or wall tiles, toilets, work surfaces, or detergents for, for example, textiles, carpets, or natural fibers. The detergents also include washing aids, which are added to the actual detergent in the manual or automatic textile washing, to another, the actual detergent not or only to an insufficient extent provided effect. Furthermore, laundry detergents within the scope of the invention also include laundry pre-treatment and aftertreatment agents, ie those agents with which the laundry item is brought into contact before or after the actual laundry, for example to dissolve stubborn stains or to achieve a soft feel and comfortable wearing behavior.

The agents may be particulate or liquid. "Liquid" means that the detergent or cleaner at room temperature, that is at about 20 ° C, in liquid form and in particular is flowable and thus can be distributed, for example, from a container.

In solid and especially in liquid agents of the invention or those used in the context of the use according to the invention or the process according to the invention, the acylhydrazone and / or the peroxidic bleach or the reducing agent may be in dissolved or suspended form; in the latter embodiment, they or at least one of them may be present in the form of powders or, if desired, conventional inert carrier materials containing granules, which may also be coated in a manner known in principle.

The use of acylhydrazones essential to the invention leads to markedly improved removal of bleachable and non-bleachable stains in the washing process at low temperatures. In addition, finetuning of stain removal performance is provided by optimizing the bleach system and saving energy through improved stain removal performance and thereby lower wash temperatures, as well as saving water by avoiding multiple washes since stains are immediately removed at the first wash.

Within the context of the use according to the invention and the process according to the invention, it is preferred if the concentration of the acylhydrazone in the especially aqueous washing or cleaning liquor, as for example in hand washing, in washing machines, but also in the cleaning of carpets or upholstery materials or when cleaning hard surfaces as tiles, tiles or dishes, which can also be done using conventional dishwashers, is used, 0.5 .mu.mol / l to 500 .mu.mol / l, in particular 5 .mu.mol / l to 100 .mu.mol / l. The concentration of manganese, titanium, cobalt, nickel or copper ions in the aqueous washing or cleaning liquor is preferably in the range from 0.1 μmol / l to 500 μmol / l, in particular 1 μmol / l to 100 μmol / l , Preferred peroxygen concentrations (calculated as H ₂ O ₂ ) in the washing or cleaning liquor are in the range from 0.001 g / l to 10 g / l, in particular from 0.1 g / l to 1 g / l and particularly preferably from 0.2 g / l to 0.5 g / l. The use according to the invention is preferably carried out at temperatures in the range from 10 ° C. to 95 ° C., in particular from 20 ° C. to below 40 ° C. The water hardness of the water used for preparing the aqueous washing or cleaning liquor is preferably in the range from 0 ° dH to 27 ° dH, in particular 0 ° dH to 21 ° dH. In the wash liquor, the water hardness is preferably in the range of 0 ° dH to 16 ° dH, in particular 0 ° dH to 3 ° dH, which can be achieved for example by the use of conventional builder materials or water softeners, if the water used to prepare the wash liquor not corresponding is soft. The use according to the invention and the method according to the invention is preferably carried out at pH values in the range from pH 5 to pH 12, in particular from pH 7 to pH 11.

The uses according to the invention and the processes according to the invention can be realized in a particularly simple manner by the use of a washing or cleaning agent according to the invention which contains an acylhydrazone or, if desired, a complex of metals obtainable by complex formation with a transition metal ion.

Detergents and cleaners which may be in the form of homogeneous solutions or suspensions in particular as pulverulent solids, in densified particle form, and which contain essential acylhydrazone or are used in the context of the uses or processes according to the invention, may in principle comprise all known ingredients customary in such agents contain. The agents may include, in particular, builders, surfactants, water, water-miscible organic solvents, bleaches, enzymes, sequestering agents, electrolytes, pH regulators, special effect polymers such as soil release polymers, dye transfer inhibitors, grayness inhibitors, wrinkle reducing polymeric agents, and polymeric builders, and others Excipients, such as optical brighteners, foam regulators, dyes and fragrances included.

Preferably in detergents or cleaners 0.001 wt .-% to 5 wt .-%, in particular 0.05 wt .-% to 2 wt .-% of said acylhydrazone contain. The indication of "% by weight" refers here and hereinafter the total weight of the composition, unless otherwise specified. It is also preferred that the agent additionally comprises a manganese, titanium, cobalt, nickel or copper salt and / or a manganese, titanium, cobalt, nickel or copper complex without a ligand which corresponds to one Acylhydrazone corresponds. Then, the molar ratio of said transition metal or the sum of said transition metals to acylhydrazone is preferably in the range of 0.001: 1 to 2: 1, especially 0.01: 1 to 1: 1. In a further preferred embodiment of agents according to the invention in these 0.05 wt .-% to 1 wt .-%, in particular 0.1 wt .-% to 0.5 wt .-% of bleach-catalyzed complex, which is a named Acylhydrazon as ligands has included. Preferred transition metal is Mn.

Suitable peroxygen compounds (peroxidic bleaches) optionally contained in the compositions are, in particular, organic peracids or persistent salts of organic acids, hydrogen peroxide and inorganic or organic compounds which release hydrogen peroxide into the washing conditions in water. Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle. Particular preference is given to using alkali metal percarbonate, alkali metal perborate monohydrate, alkali metal perborate tetrahydrate or hydrogen peroxide in the form of aqueous solutions which contain 3% by weight to 10% by weight of hydrogen peroxide. Preferably, peroxygen compounds are present in detergents or cleaners in amounts of up to 50% by weight, more preferably from 5% to 30% by weight. H ₂ O ₂ or H ₂ O ₂ releasing substances in water are preferably used as peroxidic bleaching agents, which include, in particular, alkali metal perborates, alkali metal perborates and urea perhydrate; However, it is also possible to use peroxycarboxylic acids such as diperoxodecanedicarboxylic acid or phthalimidopercaproic acid, other acids or acidic salts such as alkali persulfates or peroxodisulfates or caroates, or diacyl peroxides or tetraacyldiperoxides.

The performance of said acylhydrazones may optionally be enhanced by the presence of manganese, titanium, cobalt, nickel or copper ions, preferably Mn (II), Mn (III), Mn (IV) and / or Mn (V). -, Cu (I) -, Cu (II) - and / or Cu (III) -, Fe (I) -, Fe (II) -, Fe (III) - and / or Fe (IV), Co (I ), Co (II) and / or Co (III), Ni (I), Ni (II) and / or Ni (III), Ti (II), Ti (III) and / or or Ti (IV) ions, and more preferably selected from Mn (II) -, Mn (III) -, Mn (IV) -, Mn (V) -, Cu (I) -, Cu (II) -, Cu (III), Fe (I), Fe (II), Fe (III), Fe (IV), Co (I), Co (II) or Co (III) ions or mixtures of these, to be further strengthened; If desired, it is also possible to use complex compounds of the abovementioned metal central atoms with at least one of the abovementioned acylhydrazones as ligands. A complex which has an acylhydrazone ligand can have the corresponding ligand once or even several times, in particular twice. It can be one-or possibly two- or mehrkerning. It may also contain other neutral, anion or cationic ligands such as H ₂ O, NH ₃ , CH ₃ OH, acetylacetone, terpyridine, organic anions such as citrate, oxalate, tartrate, formate, a C _2-18 -carboxylate, a C _1-18 alkyl sulfate, especially methosulfate, or a corresponding alkanesulfonate, inorganic anions such as halide, especially chloride, perchlorate, tetrafluoroborate, hexafluorophosphate, nitrate, bisulfate, hydroxide or hydroperoxide. It may also have bridging ligands such as alkylenediamines.

In further preferred embodiments of the invention, in the presence of H ₂ O ₂ releasing peroxygen compounds, a peroxycarboxylic acid or peroxoimidic acid-forming compound is used under perhydrolysis conditions and / or a conventional bleach-activating transition metal complex compound together with the acylhydrazone. Compounds which give, under perhydrolysis conditions, optionally substituted perbenzoic acid and / or peroxycarboxylic acids having 1 to 10 C atoms, in particular 2 to 4 C atoms, are preferred. Suitable are customary bleach activators which carry O- and / or N-acyl groups, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4 dioxohexahydro-1,3,5-triazine (DADHT), acylated phenylsulfonates and carboxylates, in particular nonanoyloxy or isononanoyloxybenzenesulfonate or benzoate, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5- dihydrofuran as well as acetylated sorbitol and mannitol, and acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, as well as cationic nitrile derivatives such as trimethylammonium acetonitrile salts. Peroxycarboxylic or peroxoimidic acid-forming compound and acylhydrazone are preferably used in perhydrolysis conditions in molar ratios ranging from 4: 1 to 100: 1, more preferably from 25: 1 to 50: 1, if such are present in addition to the acylhydrazone. These optional compounds are present in detergents and cleaners, in particular in amounts of from 0.01% by weight to 10% by weight and more preferably from 1% by weight to 3% by weight. The bleach activators can be used to avoid interaction with the Bleach compounds have been coated or granulated during storage in a known manner with coating substances, wherein granulated tetraacetylethylenediamine having mean particle sizes of 0.01 mm to 0.8 mm, granulated 1,5-diacetyl-2,4-dioxohexahydro-1 with the aid of carboxymethylcellulose 3,5-triazine, and / or particulate formally prepared trialkylammonium acetonitrile is particularly preferred.

An agent may contain conventional antimicrobial agents in addition to the ingredients previously mentioned to enhance the disinfecting effect, for example against specific germs. Such antimicrobial additives are contained in disinfectants preferably in amounts of up to 10 wt .-%, in particular from 0.1 wt .-% to 5 wt .-%, but can also be completely absent, since the use of essential to the invention Acylhydrazone a significant decrease unwanted microorganisms is observed.

The agents may contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic and / or amphoteric surfactants may be included. Suitable nonionic surfactants are, in particular, alkyl glycosides and alkoxylation products of alkyl glycosides or linear or branched alcohols having in each case 12 to 18 C atoms in the alkyl moiety and 3 to 20, preferably 4 to 10, alkyl ether groups. Also suitable are the corresponding alkoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to the abovementioned alcohol derivatives with regard to the alkyl moiety and of alkylphenols having 5 to 12 C atoms in the alkyl radical.

As nonionic surfactants, in particular alkoxylated, preferably ethoxylated, especially primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) are used per mole of alcohol in which the alcohol radical can be linear or preferably methyl branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. Preferred ethoxylated alcohols include, for example, _C12-14 alcohols containing 3 EO or 4 EO, _C9-11 alcohol containing 7 EO, C _13-15 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C1 _2-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactant of the alkoxylated alcohol type is preferably present in detergents or cleaners in amounts of from 0.5% to 10% by weight, especially from 4% to 6% by weight.

Among the anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali metal ions as cations. Soaps are preferably the alkali salts of saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in incompletely neutralized form. The surfactants of the sulfate type include the salts of sulfuric acid half esters of fatty alcohols having 12 to 18 carbon atoms. Sulfonate type surfactants include alkane sulfonates of 12 to 18 carbon atoms, olefin sulfonates of 12 to 18 carbon atoms resulting from the reaction of corresponding monoolefins with sulfur trioxide, and alpha sulfo fatty acid esters useful in the sulfonation of fatty acid methyl or silane sulfonates. ethyl esters arise.

Anionic surfactants of the linear alkylbenzenesulfonate type are the salts, preferably the alkali metal salts and in particular the sodium salts of benzenesulfonic acids substituted by linear alkyl groups having from 6 to 19, preferably 7 to 15 and in particular 9 to 13 carbon atoms. A most preferred representative is sodium dodecylbenzenesulfonate. Anionic surfactant of the linear alkylbenzenesulfonate type is preferably present in detergents or cleaners in amounts of from 0.5% to 10%, and more preferably from 4% to 6%, by weight.

Anulfur-type anionic surfactants are the salts of the sulfuric acid monoesters of straight or branched C _7-21 -alcohols reacted with alkylene oxide, such as 2-methyl-branched C _9-11 alcohols containing on average 3.5 moles of ethylene oxide (EO) or Cl _2-18 fatty alcohols with 1 to 4 EO. Suitable ether sulfates are, for example, compounds of the formula R ²¹ -O- (AO) _n -SO ₃ ^- X ⁺ , in which R ^{21 is} a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably one Fatty alcohol residue, stands. Preferred radicals R ²¹ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, Nonadecyl, eicosyl and mixtures thereof, wherein the even number of C atoms are preferred. Particularly preferred radicals R ²¹ are derived from C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C ₁₀ -C ₂₀ oxo alcohols. AO represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety. The subscript n is a number in the range of 1 to 50, preferably 1 to 20 and especially 2 to 10; Most preferably, n represents numbers in the range from 2 to 8. The stated degrees of alkoxylation n are generally statistical averages, which may be an integer or a fractional number. X stands for a monovalent cation or the n-th part of an n-valent cation, the alkali metal ions being preferred, and Na ⁺ or K ⁺ being preferred, Na ^{+ being} extremely preferred. Other cations X ⁺ may be selected from NH ₄ ⁺ , ½½Zn ²⁺ , ½Mg ²⁺ , ½Ca ²⁺ , ½Mn ²⁺ , and mixtures thereof. Anionic surfactant of the ether sulfates type is preferably present in detergents or cleaners in amounts of from 1% to 10%, and more preferably from 5% to 8%, by weight.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1-6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8-28-Alkyl- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_n-T-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = -CH₂-, -O-CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist. Die kationischen Tenside weisen übliche Anionen in zum Ladungsausgleich notwendiger Art und Anzahl auf, wobei diese neben beispielsweise Halogeniden auch aus den anionischen Tensiden ausgewählt werden können. In bevorzugten Ausführungsformen kommen als kationische Tenside Hydroxyalkyl-trialkyl-ammoniumverbindungen, insbesondere C_12-18-Alkyl(hydroxyethyl)dimethylammoniumverbindungen, und vorzugsweise deren Halogenide, insbesondere Chloride, zum Einsatz. Textibehandlungsmittel enthalten bis zu 25 Gew.-%, insbesondere 0,5 Gew.-% bis 15 Gew.-% kationisches Tensid. In particular, where the compositions are those intended for the treatment of textiles, the compositions may contain, as cationic surface-active substances having a textile-softening effect, in particular one or more of the cationic, textile-softening substances of the general formulas X, XI or XII:

wherein each R ^{1 group is} independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5. The cationic surfactants have customary anions in the charge balance necessary type and number, which can be selected in addition to, for example halides also from the anionic surfactants. In preferred embodiments, the cationic surfactants used are hydroxyalkyl trialkylammonium compounds, in particular C _12-18 -alkyl (hydroxyethyl) dimethylammonium compounds, and preferably their halides, in particular chlorides. Texturing agents contain up to 25% by weight, in particular from 0.5% to 15% by weight, of cationic surfactant.

A washing or cleaning agent 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 and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular by oxidation of polysaccharides or dextrins accessible polycarboxylates, and / or polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which also small proportions Polymerizable substances without carboxylic acid functionality may contain polymerized. The relative molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200,000, those of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, in each case based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000. Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight. It is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and also vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer 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 may be a derivative of a C ₄ -C ₈ -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical. Such polymers generally have a molecular weight between 1000 and 200,000. Further preferred copolymers are those which have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate. The organic builder substances can be used, in particular for the preparation of liquid agents, 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 metal salts.

If desired, such organic builder substances may 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 stated upper limit are preferably used in pasty or liquid, in particular water-containing agents.

Suitable water-soluble inorganic builder materials are, in particular, polymeric alkali metal phosphates, which may be in the form of their alkaline neutral or acidic sodium or potassium salts. Examples of these are tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts. Crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials. used. Among these, preferred are the detergent grade crystalline sodium aluminosilicates, especially zeolite A, P and optionally X. Amounts near the above upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m. Their calcium binding capacity, according to the information of the German Patent DE 24 12 837 can be determined, is generally in the range of 100 mg to 200 mg CaO per gram.

Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates. The alkali metal silicates useful as builders 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 may be present in amorphous or crystalline form. Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na ₂ O: SiO ₂ of 1: 2 to 1: 2.8. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na ₂ Si _x O 2 _{+ x 1} · yH ₂ O are used in which x, the so-called module, a number from 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 phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates (Na ₂ Si ₂ O ₅ .yH ₂ O) are preferred. Also prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali metal silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, can be used. In a further preferred embodiment, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range 1.9 to 3.5 are used in a further preferred embodiment. In a preferred embodiment is a granular compound of alkali metal silicate and alkali, such as is available, for example under the name Nabion ^® 15 commercially. If alkali metal aluminosilicate, in particular zeolite, is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is preferably 1:10 to 10: 1. In agents containing both amorphous and crystalline alkali metal silicates, the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.

Builder substances are preferably present in detergents or cleaners in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight.

• a) 5 Gew.-% bis 35 Gew.-% Citronensäure, Alkalicitrat und/oder Alkalicarbonat, welches auch zumindest anteilig durch Alkalihydrogencarbonat ersetzt sein kann,
• b) bis zu 10 Gew.-% Alkalisilikat mit einem Modul im Bereich von 1,8 bis 2,5,
• c) bis zu 2 Gew.-% Phosphonsäure und/oder Alkaliphosphonat,
• d) bis zu 50 Gew.-% Alkaliphosphat, und
• e) bis zu 10 Gew.-% polymerem Polycarboxylat,

wobei die Mengenangaben sich auf das gesamte Wasch- beziehungsweise Reinigungsmittel beziehen. Dies gilt auch für alle folgenden Mengenangaben, sofern nicht ausdrücklich anders angegeben. In a preferred embodiment, the agent comprises a water-soluble builder block. The use of the term "builder block" is intended to express that the agents contain no further builder substances than those which are water-soluble, ie all builder substances contained in the agent are combined in the "block" characterized in this way, the amounts at most being Substances are excluded, which may be present as impurities or stabilizing additives in small amounts in the other ingredients of the products commercially. The term "water-soluble" is to be understood as meaning that the builder block dissolves without leaving a residue at the concentration which results from the use amount of the agent containing it in the customary conditions. Preferably, at least 15% by weight and up to 55% by weight, in particular 25% by weight to 50% by weight, of water-soluble builder block are contained in the compositions. This is preferably composed of the components

• a) 5% by weight to 35% by weight of citric acid, alkali citrate and / or alkali metal carbonate, which may also be replaced at least proportionally by alkali metal bicarbonate,
• b) up to 10% by weight of alkali silicate having a modulus in the range of 1.8 to 2.5,
• c) up to 2% by weight of phosphonic acid and / or alkali phosphonate,
• d) up to 50% by weight of alkali metal phosphate, and
• e) up to 10% by weight of polymeric polycarboxylate,

wherein the quantities are based on the total detergent or cleaning agent. This also applies to all following quantities, unless expressly stated otherwise.

In a preferred embodiment, the water-soluble builder block contains at least 2 of the components b), c), d) and e) in amounts greater than 0 wt .-%.

With regard to component a), in a preferred embodiment, 15% by weight to 25% by weight of alkali carbonate, which may be replaced at least proportionally by alkali metal bicarbonate, and up to 5% by weight, in particular 0.5% by weight, bis 2.5% by weight of citric acid and / or alkali citrate. In an alternative embodiment, as component a) 5 wt .-% to 25 wt .-%, in particular 5 wt .-% to 15 wt .-% citric acid and / or alkali citrate and up to 5 wt .-%, in particular 1 wt .-% to 5 wt .-% alkali carbonate, which may be at least partially replaced by alkali metal bicarbonate included. If both alkali metal carbonate and alkali metal bicarbonate are present, the component a) alkali carbonate and alkali metal bicarbonate preferably in a weight ratio of 10: 1 to 1: 1.

With regard to component b), in a preferred embodiment, 1 wt .-% to 5 wt .-% alkali silicate with a modulus in the range of 1.8 to 2.5 are included.

With regard to component c), in a preferred embodiment, from 0.05% by weight to 1% by weight of phosphonic acid and / or alkali metal phosphonate is contained. Phosphonic acids are also understood as meaning optionally substituted alkylphosphonic acids, which may also have a plurality of phosphonic acid groups (so-called polyphosphonic acids). They are preferably selected from the hydroxy and / or aminoalkylphosphonic acids and / or their alkali salts, for example dimethylaminomethane diphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethane diphosphonic acid, 1-hydroxyethane 1,1-diphosphonic acid, amino-tris (methylenephosphonic acid), N, N, N ', N'-ethylenediamine tetrakis (methylenephosphonic acid) and acylated derivatives of phosphorous acid, which can also be used in any mixtures.

With regard to component d), in a preferred embodiment, 15% by weight to 35% by weight of alkali metal phosphate, in particular trisodium polyphosphate, is contained. Alkaliphosphat is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to high molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance. Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and pass on Madrell's salt. NaH ₂ PO _{4 is} acidic; It arises when phosphoric acid with sodium hydroxide solution set a pH of 4.5 and the mash is sprayed. Potassium dihydrogen phosphate (potassium phosphate primary or monobasic potassium, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt of density 2.33 gcm ^-3 , has a melting point of 253 ° (decomposition to form (KPO ₃ ) _x , potassium polyphosphate) and is slightly soluble in water. Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm ^-3 , loss of water at 95 °), 7 moles (density 1.68 gcm ^-3 , melting point 48 ° with loss of 5H ₂ O) and 12 moles of water (density 1.52 gcm ^-3 , melting point 35 ° with the loss of 5H ₂ O), becomes anhydrous at 100 ° C. and on more intense heating passes into the diphosphate Na ₄ P ₂ O ₇ . Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is readily soluble in water. Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which have a density of 1.62 gcm ^-3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder of density 2.56 gcm ^-3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry. Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals. Na ₄ P ₂ O ₇ is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4. Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ results in higher molecular weight sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: melting or annealing phosphates, Graham's salt, Kurrolsches and Madrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates. The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or with 6H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n - Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° about 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with soda solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO ₃ ) ₃ + 2KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These are just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two applicable; It is also possible to use mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate.

With regard to component e), in a preferred embodiment, the composition contains 1.5% by weight to 5% by weight of polymeric polycarboxylate, in particular selected from the polymerization or copolymerization products of acrylic acid, methacrylic acid and / or maleic acid. Among these, the homopolymers of acrylic acid and among these in turn those having an average molecular weight in the range of 5000 D to 15000 D (PA standard) are particularly preferred.

As use in the detergents enzymes other than the above oxidase are those from the class of proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases and peroxidases and their mixtures, for example proteases such as BLAP ^®, Optimase.RTM ^®, Opticlean ^®, Maxacal ^®, Maxapem ^®, Alcalase ^®, Esperase ^®, Savinase ^®, Durazym ^® and / or Purafect ^® OxP, amylases, such as Termamyl ^®, amylase LT ^®, Maxamyl ^®, Duramyl ^® and / or Purafect ^® OxAm, lipases as Lipolase ^®, Lipomax ^®, Lumafast ^® and / or Lipozym ^®, cellulases such as Celluzyme ^® and / or Carezyme ^®. Particularly suitable are from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia derived enzymatic agents. The optionally used enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are present in detergents, cleaners and disinfectants, preferably in amounts of up to 10% by weight, in particular from 0.2% by weight to 2% by weight, particular preference being given to using enzymes which are stabilized against oxidative degradation.

In a preferred embodiment, the agent contains 5% by weight to 50% by weight, in particular 8-30% by weight of anionic and / or nonionic surfactant, up to 60% by weight, in particular 5-40% by weight. Builder and 0.2 wt .-% to 2 wt .-% enzyme selected from the proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, oxidases and peroxidases and mixtures thereof.

Among the organic solvents which can be used in the detergents and cleaners, especially if they are in liquid or pasty form, are alcohols having 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4C -Atomen, in particular ethylene glycol and propylene glycol, and mixtures thereof and derived from the classes of compounds mentioned ether. Such water-miscible solvents are preferably present in the compositions in amounts not exceeding 30% by weight, in particular from 6% by weight to 20% by weight.

To establish a desired, by the mixture of the other components not automatically resulting pH, the agents can system and environmentally acceptable acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but Also, mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are preferably contained in the compositions not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.

Soil release polymers, often referred to as "soil release" agents or because of their ability to impart soil repellency to the treated surface, for example fiber, are, for example, nonionic or cationic cellulose derivatives. The particularly polyester-active soil release polymers include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol. Preferred soil release polymers include those compounds which are formally accessible by esterification of two monomeric moieties, wherein the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR ¹¹ -) _a OH, also known as polymeric Diol H- (O- (CHR ¹¹ -) _a ) _b OH may be present. Therein, Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R ¹¹ denotes hydrogen, an alkyl radical having 1 to 22 C atoms and mixtures thereof, a is a number from 2 to 6 and b is a number from 1 to 300. Preferably, in the polyesters obtainable from these, both monomer diol units -O- (CHR ¹¹ -) _a O- and also polymeric diol units - ( O- (CHR ¹¹ -) _a ) _b O-. The molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10. In the polymer diol units, the degree of polymerization b is preferably in the range from 4 to 200, in particular from 12 to 140. The molecular weight or the maximum molecular weight distribution of preferred soil release polyesters is in the range from 250 to 100,000, in particular from 500 to 50,000 The acid underlying the radical Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferable. If desired, in place of the monomer HOOC-Ph-COOH small proportions, in particular not more than 10 mol% based on the proportion of Ph having the meaning given above, of other acids having at least two carboxyl groups may be included in the soil release-capable polyester. These include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, Maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. The preferred diols HO- (CHR ¹¹ -) _a OH include those in which R ^{11 is} hydrogen and a is a number from 2 to 6, and those in which a is 2 and R ¹¹ is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 C-atoms is selected. Among the latter diols, those of the formula HO-CH ₂ -CHR ¹¹ -OH in which R ^{11 has} the abovementioned meaning are particularly preferred. Examples of diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1, 2-dodecanediol and neopentyl glycol. Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range of 1000 to 6000. If desired, these polyesters may also be endgruppenverschlossen, with alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids in question as end groups. The ester groups bonded via end groups can be based on alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms. These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleinic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, levostearic acid, arachidic acid , Gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which may carry 1 to 5 substituents having a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-butylbenzoic acid , The end groups may also be based on hydroxymonocarboxylic acids having from 5 to 22 carbon atoms, including, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, the hydrogenation product of which include hydroxystearic acid and also o-, m- and p-hydroxybenzoic acid. The hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group. Preferably, the number of hydroxymonocarboxylic acid units per end group, that is to say their degree of oligomerization, is in the range from 1 to 50, in particular from 1 to 10. In a preferred embodiment of the invention, polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 to 5,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, used alone or in combination with cellulose derivatives.

In particular, suitable for use in laundry detergents of textiles color transfer inhibitors include polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole and optionally other monomers.

The means for use in textile laundry may contain anti-wrinkling agents, since textile fabrics, in particular of rayon, wool, cotton and their mixtures, may tend to wrinkle, because the individual fibers are sensitive to bending, buckling, pressing and squeezing transverse to the fiber direction. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, -alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

Graying inhibitors have the task of keeping suspended from the hard surface and in particular from the textile fiber suspended dirt in the fleet. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, other than the above-mentioned starch derivatives can be used, for example aldehyde starches. Preference is given to using cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions.

The agents may contain optical brighteners, among these in particular derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which, instead of the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Further, brighteners of the substituted diphenylstyrene type may be present, for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned optical brightener can be used.

In particular when used in automatic washing or cleaning processes, it may be advantageous to add conventional foam inhibitors to the compositions. As foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silicic acid or bis-fatty acid alkylenediamides. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes. The foam inhibitors, in particular silicone- and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamide are preferred.

In addition, agents can be used to prevent the tarnishing of silver objects, so-called silver corrosion inhibitors. Preferred silver corrosion inhibitors are organic disulfides, dihydric phenols, trihydric phenols, optionally alkyl- or aminoalkyl-substituted triazoles such as benzotriazole and cobalt, manganese, titanium, zirconium, hafnium, vanadium or cerium salts and / or complexes in which the Metals in one of the oxidation states II, III, IV, V or VI are present.

The abovementioned acylhydrazones can be present in the form of powders or as granules, which may also optionally be coated and / or dyed and may contain conventional carrier materials and / or granulation auxiliaries. In the case of their use as granules, if desired, these may also contain further active substances, in particular bleach activator.

The preparation of solid agents presents no difficulties and can be carried out in a manner known in the art, for example by spray-drying or granulation, with sensitive ingredients such as peroxygen compound, enzyme or bleach activator optionally being added later. For producing the compositions having an increased bulk density, in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred. Detergents, cleaners or disinfectants in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer. In a preferred embodiment of means for the particular machine cleaning of dishes, these are tablet-shaped. Examples Example 1: Preparation of

17.8 g of 4- (2-hydrazinyl-2-oxoethyl) -4-methylmorpholine-4-ium were dissolved in 100 ml of methanol. At room temperature, 7.5 g of pyridine-2-carbaldehyde were added dropwise with stirring, whereby the solution turned yellow. After stirring at room temperature for 18 h, the mixture was stirred for a further 7 h with heating to boiling under reflux. Subsequently, the solvent was removed on a rotary evaporator. After drying with an oil pump vacuum, 24.4 g of P1 were obtained as a yellow solid.

1 H-NMR (DMSO, 100 MHz) δ (ppm): 3.45 (s, 3H); 3.7-3.9 (m, 4H); 4.0 (m, 4H); 4.6 and 5.0 (2s, 1H); 7.5 (m, 1H); 7.9 (m, 1H); 8.1 (m, 1H), 8.2 and 8.4 (2s, 1H); 8.1 and 7.9 (2d, 1H), 8.6 and 8.6 (2s, 1H), 12.2 and 12.6 (2s, 1H).

Example 2: Washing tests

For the measurement of the primary washing performance, textile cotton substrates which had been provided with the standardized soiling indicated in the table below, at the temperature also indicated in the table with a wash liquor containing 3.8 g / l of a particulate detergent with 11.5 wt. % Sodium percarbonate and 3.5% by weight TAED (V1), with one otherwise like V1 composed, but additionally 0.008 g / l of the prepared in Example 1 morpholinium 4- (2- (2 - ((2-pyridinylmethyl) methylene) hydrazinyl) -2-oxoethyl) -4-methyl bromide P1 containing wash liquor ( M1), with a wash liquor containing 4.1 g / l of a bleach-and bleach-activator-free liquid detergent (V2), with a wash liquor (M2) otherwise composed as V2 but additionally containing 0.08 g / l P1 or with an otherwise like M2 washed, but also also containing 0.08 g / l hydroxylamine hydrochloride washing solution (M3). The treated fabric substrates were subsequently dried and color-measured to determine the Y value (brightness value). The table below shows the difference in the brightness values of cotton gauges before and after washing (mean value of 6-fold determinations). Table 1: Washing performance medium temperature soiling .DELTA.Y V1 40 ° C Blood / milk / ink 31.2 M1 40 ° C Blood / milk / ink 35.5 V1 40 ° C blood 61.6 M1 40 ° C blood 77.5 V1 20 ° C Blood / milk / ink 39.7 M1 20 ° C Blood / milk / ink 45.8 V1 20 ° C blood 77.3 M1 20 ° C blood 81.5 V2 40 ° C bilberry 24.8 M2 40 ° C bilberry 25.6 M3 40 ° C bilberry 28.3

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been 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.

Cited patent literature

• WO 2009/124855 [0003]
• WO 2012/080088 [0003]
• DE 2412837 [0040]

Claims (10)

Acylhydrazone of general formula I,

in the R ^{1 is} a CF ₃ or an optionally substituted C _1-28 alkyl, C _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 Cycloalkenyl, phenyl, naphthyl, C _7-9 -aralkyl, C _3-20 -heteroalkyl or C _3-12 -cycloheteroalkyl, one of R ² and R ^{3 is} an optionally substituted pyridine group and the other of the radicals R ² and R ^{3 are} hydrogen or an optionally substituted C _1-28 -alkyl, C _2-28 -alkenyl, C _2-22 -alkynyl, C _3-12 -cycloalkyl, C _3-12 -cycloalkenyl, C _7-9 aralkyl, C _3-28 heteroalkyl, C _3-12 cycloheteroalkyl, C _5-16 heteroaralkyl, phenyl, naphthyl or heteroaryl, and R ^{4 is} hydrogen or C _{1-6 28} alkyl, C _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 cycloalkenyl, C _7-9 aralkyl, C _3-20 - Heteroalkyl, C _3-12 cycloheteroalkyl, C _5-16 heteroaralkyl group or an optionally substituted phenyl or naphthyl or heteroaryl group. Use of an acylhydrazone of the general formula I,

in the R ^{1 is} a CF ₃ or an optionally substituted C _1-28 alkyl, C _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 Cycloalkenyl, phenyl, naphthyl, C _7-9 -aralkyl, C _3-20 -heteroalkyl or C _3-12 -cycloheteroalkyl, one of R ² and R ^{3 is} an optionally substituted pyridine group and the other of the radicals R ² and R ^{3 are} hydrogen or an optionally substituted C _1-28 -alkyl, C _2-28 -alkenyl, C _2-22 -alkynyl, C _3-12 -cycloalkyl, C _3-12 -cycloalkenyl, C _7-9 aralkyl, C _3-28 heteroalkyl, C _3-12 cycloheteroalkyl, C _5-16 heteroaralkyl, phenyl, naphthyl or heteroaryl, and R ^{4 is} hydrogen or C _{1-6 28} alkyl, C _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 cycloalkenyl, C _7-9 aralkyl, C _3-20 Heteroalkyl, C _3-12 -cycloheteroalkyl, C _5-16 -Heteroaralkylgruppe or an optionally substituted phenyl or naphthyl or heteroaryl group, to improve the Dirt removal performance of detergents or cleaning agents in their application. Use according to claim 2, characterized in that the acylhydrazone is used in combination with a peroxidic bleach. Use according to claim 2, characterized in that the acylhydrazone is used in combination with a reducing agent. Use of an acylhydrazone of the general formula I,

in the R ^{1 is} a CF ₃ or an optionally substituted C _1-28 alkyl, C _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 Cycloalkenyl, phenyl, naphthyl, C _7-9 -aralkyl, C _3-20 -heteroalkyl or C _3-12 -cycloheteroalkyl group, one of the radicals R ² and R ^{3 is} an optionally substituted pyridine group and the other of the radicals R ² and R ^{3 is} hydrogen or an optionally substituted C _1-28 alkyl, C _2-28 alkenyl, C _2-22 Alkynyl, C _3-12 -cycloalkyl, C _3-12 -cycloalkenyl, C _7-9 -aralkyl, C _3-28 -heteroalkyl, C _3-12 -cycloheteroalkyl, C _5-16 -heteroaralkyl- , Phenyl, naphthyl or heteroaryl group, and R ^{4 is} hydrogen or a C _1-28 alkyl, C _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _{3 -12} -cycloalkenyl, C _7-9 -aralkyl, C _3-20 -heteroalkyl, C _3-12 -cycloheteroalkyl, C _5-16 -heteroaralkyl or an optionally substituted phenyl or naphthyl or heteroaryl group, to Improvement of the bleaching performance of peroxide bleaching agents in detergents or cleaners in their application. Process for removing stains from textile or hard surfaces by contacting the stained surface with an aqueous preparation, the acylhydrazone of general formula I,

in the R ^{1 is} a CF ₃ or an optionally substituted C _1-28 alkyl, C _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 Cycloalkenyl, phenyl, naphthyl, C _7-9 -aralkyl, C _3-20 -heteroalkyl or C _3-12 -cycloheteroalkyl, one of R ² and R ^{3 is} an optionally substituted pyridine group and the other of the radicals R ² and R ^{3 are} hydrogen or an optionally substituted C _1-28 -alkyl, C _2-28 -alkenyl, C _2-22 -alkynyl, C _3-12 -cycloalkyl, C _3-12 -cycloalkenyl, C _7-9 aralkyl, C _3-28 heteroalkyl, C _3-12 cycloheteroalkyl, C _5-16 heteroaralkyl, phenyl, naphthyl or heteroaryl, and R ^{4 is} hydrogen or C _{1-6 28} alkyl, C _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 cycloalkenyl, C _7-9 aralkyl, C _3-20 Heteroalkyl, C _3-12 cycloheteroalkyl, C _5-16 heteroaralkyl group or an optionally substituted phenyl or naphthyl or heteroaryl group. A method according to claim 6, characterized in that the aqueous preparation contains peroxidic bleach. A method according to claim 6, characterized in that the aqueous preparation contains reducing agent. Washing or cleaning compositions containing an acylhydrazone of general formula I,

in the R ^{1 is} a CF ₃ or an optionally substituted C _1-28 alkyl, C _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 Cycloalkenyl, phenyl, naphthyl, C _7-9 -aralkyl, C _3-20 -heteroalkyl or C _3-12 -cycloheteroalkyl, one of R ² and R ^{3 is} an optionally substituted pyridine group and the other of the radicals R ^2, and R ³ represents hydrogen or an optionally substituted C _1-28 alkyl, C _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 cycloalkenyl, C _7-9 aralkyl, C _3-28 heteroalkyl, C _3-12 cycloheteroalkyl, C _5-16 heteroaralkyl, phenyl, naphthyl or heteroaryl, and R ^{4 is} hydrogen or C _{1-6 28} alkyl, C _2-28 alkenyl, C 2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 cycloalkenyl, C _7-9 aralkyl, C _3-20 heteroalkyl -, C _3-12 -cycloheteroalkyl, C _5-16 heteroaralkyl or an optionally substituted phenyl or naphthyl or heteroaryl group. Acylhydrazone of claim 1, use according to any one of claims 2 to 5, Method according to one of claims 6 to 8, or composition according to claim 9, characterized in that the acylhydrazone of the general formula (II),

in the R ^{1 is} a C _1-4 alkyl group having a substituent

in which R ^{10 represents} hydrogen or a C _1-28 -alkyl, C _2-28 -alkenyl, C _2-22 -alkynyl, C _3-12 -cycloalkyl, C _3-12 -cycloalkenyl-, C _7-9 aralkyl, C _3-20 heteroalkyl, C _3-12 cycloheteroalkyl, _5-16 -Heteroaralkylgruppe a and C ^- is the anion of an organic or inorganic acid, R ² and R ⁴ for Formula (I) and R ⁵ , R ⁶ , R ⁷ and R ^{8 are} independently R ¹ , hydrogen, halogen, a hydroxy, amino, an optionally substituted N-mono or di-C _1-4 alkyl or C _2-4 hydroxyalkylamino, N-phenyl or N-naphthylamino, C _1-28 alkyl, C _1-28 alkoxy, phenoxy, C _2-28 Alkenyl, C _2-22 -alkynyl, C _3-12 -cycloalkyl, C _3-12 -cycloalkenyl, C _7-9 -aralkyl, C _3-20 -heteroalkyl, C _3-12 -cycloheteroalkyl- , C _5-16 heteroaralkyl, phenyl or naphthyl, wherein the substituents are selected from C _1-4 alkyl, C _1-4 alkoxy, hydroxy, sulfo, sulfato, halo, cyano , Nitro, carboxy, Phenyl, phenoxy, naphthoxy, amino, N-mono- or di-C _1-4 -alkyl or C _2-4 -hydroxyalkylamino, N-phenyl or N-naphthylamino groups, or R ⁵ and R ⁶ or R ⁶ and R ⁷ or R ⁷ and R ⁸ to form 1, 2 or 3 carbocyclic or O, NR ¹⁰ - or S-heterocyclic, optionally aromatic and / or optionally C _1-6 alkyl-substituted rings connected to each other.