WO2017102475A1

WO2017102475A1 - Pyridine group-containing acyl hydrazones

Info

Publication number: WO2017102475A1
Application number: PCT/EP2016/079984
Authority: WO
Inventors: Christian Kropf; Thomas Gerke; André HÄTZELT
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2015-12-18
Filing date: 2016-12-07
Publication date: 2017-06-22
Also published as: DE102015225880A1

Abstract

The aim of the invention is to improve the cleaning power of detergents and cleaning agents in relation to stains. This is substantially achieved by incorporating pyridine group-containing acyl hydrazones.

Description

Pyridine group-containing acylhydrazones

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 their performance to be satisfactory

Detergent. High washing temperatures are also associated with increased energy consumption, which is to be avoided due to environmental protection and resource conservation.

International patent application WO 2009/124855 discloses metal complexes with acyl hydrazone ligands which carry electron-withdrawing substituents in the vicinity of the acyl group. 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.

An object of the present invention are acylhydrazones of general formula I,

in the R is a CF3 or an optionally substituted Ci-28-alkyl, C2 alkenyl, C2-22 alkynyl, -i2-cycloalkyl, -i2-cycloalkenyl, phenyl, naphthyl, -9 Aralkyl, -2o-heteroalkyl or -i2-cycloheteroalkyl group,

one of the radicals R ² and R ^{3 is} an optionally substituted pyridine and the other of the radicals R ² and R ^{3 is} hydrogen or an optionally substituted Ο-28-alkyl, C2-alkenyl, C2-22-alkynyl, -i2 Cycloalkyl, -i2-cycloalkenyl, -9-aralkyl, -heteroalkyl, -12-cycloheteroalkyl, -i6-heteroaralkyl, phenyl, naphthyl or heteroaryl group, and

R ^{4 is} hydrogen or a C 1 -28-alkyl, C 2 -alkenyl, C 2-12 -alkynyl, -i 2 -cycloalkyl, -12-cycloalkenyl, -9-aralkyl, -2o-heteroalkyl-, i2-cycloheteroalkyl, -i6-heteroaralkyl or an optionally substituted phenyl or naphthyl or heteroaryl group

stand.

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 of removing soils from textile or hard surfaces by contacting the soiled 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 dirt removal performance of detergents or cleaning agents in their use, and a method for removing stains from textile or hard surfaces by contacting the soiled surface with an aqueous preparation, containing such acylhydrazone. The improvement in the 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 subject invention described above 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 as hydrochloride, ascorbic acid, ascorbic acid alkali metal salts, isoascorbic acid, isoascorbic acid alkali metal salts, alkali metal sulphites, alkali hydrogen sulphites, aldehydes such as hydroxypropanedial, and mixtures of two or more of this. 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 soils 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 Ν, Ν, Ν ', Ν'-tetraacetylethylenediamine, for example be removed 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, which contain 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 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.

Preferred embodiments of the acylhydrazones include those of the general formula (II),

in the R for a Ο-4-alkyl group having a substituent

in which R ^{0 is} hydrogen or a Ο-28-alkyl, C 2-30 alkenyl, C 2-22 alkynyl, C 3-12 cycloalkyl, C 3-12 cycloalkenyl, C 7-9 aralkyl -, C3-2o-heteroalkyl, C3-i2-cycloheteroalkyl, C5-16 heteroaralkyl and A ^"represents the anion of an organic or inorganic acid, R ² and R ^{4 have} the meaning given for formula (I) and

R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently R, hydrogen, halogen, hydroxy, amino, optionally substituted N-mono or di-O-4-alkyl or C 2-4 hydroxyalkylamino -, N- Phenyl or N-naphthyl-amino, C-28-alkyl, C-28-alkoxy, phenoxy, C 2-30 -alkenyl, C 2-22 -alkynyl, C 3-12 -cycloalkyl-, C 3- i2-cycloalkenyl, Cz-g-aralkyl, C3-2o-heteroalkyl, C3-i2-cycloheteroalkyl, C5-16 heteroaralkyl, phenyl or naphthyl group, wherein the substituents are selected from Ci-4-alkyl -, hydroxy, sulfo, sulfato, halogen, cyano, nitro, carboxy, phenyl, phenoxy, naphthoxy, amino, N-mono or di-Ci-4-alkyl or C2 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.

10

R

-NO

Particularly preferred is the presence of the substituent \ /

The anion A ^"is preferably carboxylate such as lactate, citrate, tartrate or succinate, perchlorate, rafluoroborat Tet, hexafluorophosphate, alkyl sulfonate, alkyl sulfate, hydrogen sulfate, sulfate, phosphate dihydrogen, hydrogen phosphate, phosphate, isocyanate, thiocyanate, 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 laundry, in order to achieve a further, not provided by the actual detergent or only insufficiently provided effect. Furthermore, detergents are also included within the scope of the invention Prewash and aftertreatment agents, ie those agents with which the garment is brought into contact before or after the actual wash, for example, to solve stubborn stains or to achieve a soft touch and comfortable wearing.

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 the stain removal performance is achieved by optimizing the bleaching system and saving energy through improved stain removal performance and consequently lower washing temperatures, as well as water saving by avoidance of multiple washes, since stains are immediately removed on 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 μιηοΙ / Ι to 500 μιηοΙ / Ι, in particular 5 μιηοΙ / Ι to 100 μιηοΙ / Ι is. Preferably, the concentration of manganese, titanium, cobalt, nickel or copper ions in the aqueous washing or cleaning liquor in the range of 0.1 μιηοΙ / Ι to 500 μιηοΙ / Ι, in particular 1 μιηοΙ / Ι to 100 μιηοΙ / Ι , 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 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 is not correspondingly 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 1 1.

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 be, in particular, builders, surfactants, water, water-miscible organic solvents, bleaches, enzymes, sequestering agents, electrolytes, pH regulators, polymers with special effects, such as soil release polymers, dye transfer inhibitors, grayness inhibitors, wrinkle-reducing polymeric agents and form-retaining polymers Active ingredients, and other auxiliaries, 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 term "% by weight" here and below refers to the total weight of the composition, unless stated otherwise, and it is also preferable that the agent additionally contains a manganese, titanium, cobalt, nickel or copper salt and / or a manganese, titanium, cobalt, nickel or copper complex without a ligand corresponding to said acylhydrazone, 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, in particular 0.01: 1 to 1: 1. In a further preferred embodiment of compositions according to the invention, 0.05 to 1% by weight, in particular 0.1 to 1% by weight, are present therein. % to 0.5% by weight of a bleach-catalyzed complex having a named acylhydrazone as a ligand 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, that is to say an oxidase and its substrate become. 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. The peroxide bleaching agents used are preferably H2O2 or water-releasing substances, in particular alkali perborates, alkali metal peracids 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 (l ), Co (II) and / or Co (III), Ni (I), Ni (II) and / or Ni (III), Ti (II), Ti (III), and / 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, if appropriate, two or more nuclei. It may also contain other neutral, anion or cationic ligands such as H2O, NH3, CH3OH, acetylacetone, terpyridine, organic anions such as citrate, oxalate, tartrate, formate, a C2-is carboxylate, a C18-alkyl sulfate , in particular methosulfate, or a corresponding alkanesulfonate, inorganic anions such as, for example, halide, in particular chloride, perchlorate, tetrafluoroborate, hexafluorophosphate, nitrate, hydrogensulfate, hydroxide or hydroperoxide. It may also have bridging ligands such as alkylenediamines.

In further preferred embodiments of the invention, in the presence of H2O2-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 is used together with the acylhydrazone. Compounds which give, under perhydrolysis conditions, optionally substituted perbenzoic acid and / or peroxocarboxylic acids having 1 to 10 C atoms, in particular 2 to 4 C atoms, are preferred. Suitable bleach activators are those which carry O- and / or N-acyl groups, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated glycerol colouristic, 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 isononanoyloxy-benzenesulfonate or benzoate, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran, and acetylated sorbitol and mannitol, and acylated sugar derivatives, especially pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose, and acetylated, optionally N -alkylated glucamine and gluconolactone, as well as cationic nitrile derivatives such as trimethylammonium acetonitrile salts. Peroxycarboxylic acid or peroxoimidic acid-forming compound and acylhydrazone are preferably used in perhydrolysis conditions in molar ratios in the range from 4: 1 to 100: 1, in particular 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 may have been coated or granulated in a known manner with coating substances in order to avoid the interaction with the bleach compounds, granulated tetraacetylethylenediamine having average particle sizes of from 0.01 mm to 0.8 mm, granulated 1 with the aid of carboxymethyl cellulose, 5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and / or in particulate form, 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 are in particular alkoxylated, preferably ethoxylated, especially primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 mol ethylene oxide (EO) per mole of alcohol used in which the alcohol radical linear or preferably methyl branched in the 2-position may be linear or methyl-branched radicals in the mixture. th, 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. The preferred ethoxylated alcohols include, for example, C12-14-alcohols with 3 EO or 4 EO, Cg-n-alcohol with 7 EO, cis-is alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2-i8- Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci2-i4-alcohol with 3 EO and Ci2-is-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 rank 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%, and more preferably 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. The sulfonate-type surfactants include alkane sulfonates having 12 to 18 carbon atoms, olefin sulfonates having 12 to 18 carbon atoms, which are formed in the reaction of corresponding monoolefins with sulfur trioxide, and alpha-sulfofatty acid esters which are active in the sulfonation of fatty acid methyl sulfonates. or 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-chain or branched C7-2i-alcohols reacted with alkylene oxide, such as 2-methyl-branched C9-11-alcohols having on average 3.5 moles of ethylene oxide (EO) or Ci2-is Fatty alcohols with 1 to 4 EO. Suitable ether sulfates are, for example, compounds of the formula R ² -O- (AO) _n -SO 3 ^" X ⁺ in which R ^{2 is} a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical Preferred radicals R ² are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, Pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and mixtures thereof, with the even number of carbon atoms being preferred. Particularly preferred radicals R ² are derived from C 12-18 fatty alcohols, for example coconut oil fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C 10 C 20 oxo alcohols. AO is an ethylene oxide (EO) or propylene oxide (PO) grouping, preferably an ethylene oxide grouping. 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 is a monovalent cation or the nth part of an n-valent cation, with preference being given to the alkali metal ions and, below this, Na ⁺ or K ⁺ , Na ^{+ being} extremely preferred. Other cations X ⁺ may be selected from NhV, Zn Mg ²⁺ , V ₂ Ca ²⁺ y ₂ Mn 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.

The compositions may, in particular if they are those which are intended for the treatment of textiles, as cationic surface-active substances with textile softening effect in particular one or more of the cationic, fabric softening substances of the general formulas X, XI or XII contain:

R ¹

(X)

R ¹

R is -N ⁽⁺⁾ - (CH ₂ ) n -CH-CH ₂ (XI)

I II

R T T

I i

R ² R ²

R ¹

R ³ -N < ⁺ L (CH ₂ ) n TR ² (XII)

I

R ⁴ in which each R group is independently selected from C 1-6 -alkyl, -alkenyl or -hydroxyalkyl groups; each group R ^{2 is} independently selected from Cs-28-alkyl or alkenyl groups; R ³ = R or (CH ₂₎ NTR ^2; R ⁴ = R 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 also polymeric (poly) carboxylic acids, in particular polycarboxylates obtainable by oxidation of polysaccharides or dextrins, and / or polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers thereof, which also contain small amounts of polymerizable substances may contain copolymerized without carboxylic acid functionality. The molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, each based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight. Terpolymers which contain two unsaturated acids and / or their salts as monomers and also vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer may also be used as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C3-Cs-carboxylic acid and preferably from a C3-C4-monocarboxylic acid, in particular from (meth) -acrylic acid. The second acidic monomer or its salt may be a derivative of a C4-Cs-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 1,000 and 200,000. Further preferred copolymers are those which have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate. The organic builders may, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 weight percent aqueous solutions be used. 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. Quantities near the upper limit mentioned are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 μm, and preferably consist of at least 80% by weight of particles having a size of less than 10 μm. Their calcium binding capacity, which can be determined according to the specifications of the German patent DE 24 12 837, 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 from 1: 2 to 1: 2.8. Crystalline silicates which may be present alone or in a mixture with amorphous silicates are preferably crystalline phyllosilicates of the general formula Na.sub.2SixO.sub.2.sup.x + H.sub.2O.sub.2, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 is up 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 y H 2 O) is preferred. Also prepared from amorphous alkali silicates, practically anhydrous crystalline alkali silicates of the above 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 is sand and soda can be produced. Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5 are used in a further preferred embodiment. In a preferred embodiment, a granular compound of alkali metal silicate and alkali carbonate is used, as it is commercially available, for example, under the name Nabion® 15. If alkali metal silicate, in particular zeolite, is 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 compositions which contain both amorphous and crystalline alkali metal silicates the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate 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.

In a preferred embodiment, the agent comprises a water-soluble builder block. By using the term "builder block", it 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 Amounts of substances are excluded, which may be commercially available as impurities or stabilizing additives in small amounts in the other ingredients of the funds. 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 of the agent containing it under the usual conditions, preferably at least 15% by weight and up to 55% by weight %, in particular 25 wt .-% to 50 wt .-% of water-soluble builder block contained in the agents.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% by weight to 5% by weight of alkali metal silicate with a modulus in the range from 1.8 to 2.5 are contained.

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'-ethylenediaminetrakis (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 (HP03) n and orthophosphoric H3PO4 in addition to higher 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, NaH2PÜ4, exists as a dihydrate (density 1, 91 like ³ , melting point 60 °) and as a monohydrate (density 2.04 like ³ ). Both salts are white, very soluble in water powders, which lose the water of crystallization on heating and at 200 ° C in the weak acid diphosphate (disodium hydrogenated diphosphate, ΝΒΣΗΣΡΣΟ), at higher temperature in sodium trimetaphosphate (Na3P3Ü9) and Madrell's salt. NaH2PÜ4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH2PO4, is a white salt of density 2.33 likes ³ , has one Melting point 253 ° (decomposition to form (KP03) x, potassium polyphosphate) and is readily 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 like ³ , water loss at 95 °), 7 moles (density 1, 68 like ³ , melting point 48 ° with loss of 5 H2O) and 12 moles water (density 1, 52 preferably ³ , melting point 35 ° with loss of 5H 2 O), becomes anhydrous at 100 ° C. and on more intense heating passes into the diphosphate Na 4P 2 O. 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), K2HPO4, is an amorphous, white salt that is readily soluble in water. Trisodium phosphate, tertiary sodium phosphate, NasPC, are colorless crystals which have a density of 1, 62, ³ and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P2O5) as the dodecahydrate Melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P2O5) has a density of 2.536 like 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 trisubstituted potassium phosphate), K3PO4, is a white, deliquescent, granular powder of density 2.56, ³ , with 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. Tetra sodium diphosphate (sodium pyrophosphate), Na4P20, exists in anhydrous form (density 2.534, ³ , melting point 988 °, also indicated 880 °) and as decahydrate (density 1, 815-1, 836, ³ , melting point 94 ° with loss of water). For substances are colorless, in water with alkaline reaction soluble crystals. Na4P20 is formed by heating disodium phosphate to> 200 ° C 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), K4P2O7, exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33% ³ , which is soluble in water, the pH of the 1% solution being 25 ° 10, 4 is. Condensation of the NaH2PÜ4 or KH2PO4 leads to higher molecular weight sodium and potassium phosphates, which can be used to distinguish cyclic representatives, the sodium and potassium metaphosphates, and the chain-like types, the sodium and 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 industrially important pentasodium triphosphate, NasPsO-io (sodium tripolyphosphate), is anhydrous or water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n- Na, which crystallizes with 6H 2 O, and which is non-hygroscopic n =. 3 In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution By hydrolysis to about 100%, about 8% orthophosphate and 15% diphosphate are formed. 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, K5P3O10 (Kaliumtnpolyphosphat), for example, in the form of a 50 wt .-% solution (> 23% P2O5, 25% K2O) 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 hydrolyzing sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH Na ₃ K ₂ P 30io + 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 agent contains from 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, particularly preferred are the homopolymers of acrylic acid and, among these, those having an average molecular weight in the range from 5,000 D to 15,000 D (PA standard).

As enzymes which can be used in the compositions, apart from the abovementioned oxidase, those from the class of the proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases and peroxidases and mixtures thereof are suitable, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Alcalase®, Esperase®, Savinase®, Durazym® and / or Purafect® OxP, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or Purafect® OxAm, lipases such 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 preferably used in detergents, cleaners and disinfectants in amounts of up to 10 wt .-%, in particular from 0.2 wt .-% to 2 wt .-%, with particular preference against oxidative degradation stabilized enzymes are used.

In a preferred embodiment, the composition 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 -Ato- men, in particular ethylene glycol and propylene glycol, and mixtures thereof and derived from the said classes of compounds ethers. 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, not by itself resulting from the mixture of the other components of the pH, the agents systemic and environmentally friendly acids, especially 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 not more than 20 wt .-%, in particular from 1, 2 wt .-% to 17 wt .-%, contained in the means.

Soil release polymers, which are often referred to as "soil release" agents or because of their ability to render the treated surface, for example fiber, soot repellent, are, for example, nonionic or cationic cellulose derivatives Degreasing-rich 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 The preferred soil release polymers include those compounds which are formally accessible by esterification of two monomer parts. wherein the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR-) _a OH, which may also be present as a polymeric diol H- (O- (CHR-) _a ) t _> OH. Therein Ph is an o-, m- or p-phe nylenrest, which may carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R is hydrogen, an alkyl radical having 1 to 22 carbon atoms and mixtures thereof, a is a number of 2 to 6 and b is a number from 1 to 300. Preferably, in the these polyester available both Monomerdioleinheiten -0- (CHR -) _a O- and Polymerdiol- units - (0- (CHR -) _a ) bO- before. 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 average molecular weight or the maximum of the molecular weight distribution of preferred soil release polymers 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, mililitic 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. Preferred diols HO- (CHR-) _a OH include those in which R is hydrogen and a is a number from 2 to 6, and those in which a is 2 and R is hydrogen and the alkyl radicals have from 1 to 10 , in particular 1 to 3 C-atoms is selected. Among the latter diols, those of the formula HO-CH 2 -CHR -OH in which R 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, undecanic 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 , Elaeostearic acid, arachidic acid, gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, the 1 to 5 substituents having a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms can carry, 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 hydroxymono- For their part, carboxylic acids can be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group. The number of hydroxymonocarboxylic acid units per end group, that is to say their degree of oligomerization, is preferably 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 Molar weights of 750 to 5000 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.

Suitable color transfer inhibitors for use in laundry detergents include, in particular, 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 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 means used.

The agents may contain optical brighteners, among these in particular derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or similarly constructed compounds which are substituted for the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. WEI Furthermore, 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) -diphenyls. 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 Ci8-C24 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. Preferably, the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamide are preferred.

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, these may, if desired, 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 oil pump vacuum, 24.4 g of P1 were obtained as a yellow solid.

Ή-NMR (DMSO; 100 MHz) 5 (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 stains given 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 % Of sodium percarbonate and 3.5% by weight of TAED (V1), with an otherwise composed as V1, but in addition 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 an otherwise as V2 combined, but in addition 0.08 g / l P1 containing wash liquor (M2) or washed with a otherwise composed as M2, but also also 0.08 g / l hydroxylamine hydrochloride containing wash liquor (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

Mean temperature soiling ΔΥ

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 blueberry 24.8

M2 40 ° C blueberry 25.6

M3 40 ° C Blueberry 28.3

Claims

claims

1. Acylhydrazone of the general formula I,

in the R is a CF3 or an optionally substituted Ο-28-alkyl, C2-28 alkenyl, C2-22 alkynyl, C3-i2-cycloalkyl, C3-i2-cycloalkenyl, phenyl, naphthyl C7-9 aralkyl, C3-20 heteroalkyl or C3-i2 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 Ο-28-alkyl, C 2-30 alkenyl, C 2-22 alkynyl, C 3-12 cycloalkyl, C 3-12 cycloalkenyl, C 7-9 aralkyl, C 3-18 heteroalkyl, C 3-12 cycloheteroalkyl, C 5-16 heteroaralkyl, phenyl, naphthyl or heteroaryl group, and R ^{4 is} hydrogen or C 1 -C 28 alkyl, C 2-28 alkenyl, C 2-22 alkynyl, C 3 -12 cycloalkyl, C 3-12 cycloalkenyl, C 7-9 aralkyl, C 3 -2o-heteroalkyl, C3-i2-cycloheteroalkyl, C5-16 heteroaralkyl group or an optionally substituted phenyl or naphthyl or heteroaryl group

stand.

2. Use of an acylhydrazone of the general formula I,

in the R is a CF3 or an optionally substituted Ci-28-alkyl, C2-28 alkenyl, C2-22 alkynyl, C3-i2-cycloalkyl, C3-i2-cycloalkenyl, phenyl, naphthyl C7-9 aralkyl, C3-20 heteroalkyl or C3-i2 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 2-30 alkenyl, C 2-22 -alkynyl, C 3-12 cycloalkyl, C 3-12 cycloalkenyl, C 7-9 aralkyl, C 3-18 heteroalkyl, C 3-12 cycloheteroalkyl, C 5-16 heteroaralkyl, phenyl, naphthyl or heteroaryl group, and R ^{4 is} hydrogen or C 1 -C 28 alkyl, C 2-28 alkenyl, C 2-22 alkynyl, C 3 -12 cycloalkyl, C 3-12 cycloalkenyl, C 7-9 aralkyl, C 3 -2o-heteroalkyl, C3-i2-cycloheteroalkyl, C5-16 heteroaralkyl group or an optionally substituted phenyl or naphthyl or heteroaryl group to improve the dirt removal performance of detergents or cleaners 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,

to improve the bleaching performance of peroxide bleach in laundry detergents or cleaners when they are used.

Process for removing stains from textile or hard surfaces by contacting the polluted surface with an aqueous preparation, the acylhydrazone of general formula I,

stand, contains.

7. The method according to claim 6, characterized in that the aqueous preparation contains peroxidic bleach.

8. The method according to claim 6, characterized in that the aqueous preparation contains reducing agent.

9. Was - or cleaning agent, containing an acylhydrazone of the general formula I,

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 2-30 alkenyl, C 2-22 -alkynyl, C 3-12 cycloalkyl, C 3-12 cycloalkenyl, C 7-9 aralkyl, C 3-18 heteroalkyl, C 3-12 cycloheteroalkyl, C 5-16 heteroaralkyl, phenyl, naphthyl or heteroaryl group, and R ^{4 is} hydrogen or C 1 -C 28 alkyl, C 2-28 alkenyl, C 2-22 alkynyl, C 3 -12 cycloalkyl, C 3-12 cycloalkenyl, C 7-9 aralkyl, C 3 -2o-heteroalkyl, C3-i2-cycloheteroalkyl, C5-16 heteroaralkyl group or an optionally substituted phenyl or naphthyl or heteroaryl group

stand.

10. acylhydrazone according to claim 1, use according to one of claims 2 to 5, method according to one of claims 6 to 8, or agent according to claim 9, characterized in that the acylhydrazone corresponds to the general formula (II),

in the R for a Ci-4-alkyl group which is a substituent

in which R ^{0 is} hydrogen or C 1 -C 28 -alkyl, C 2-28 alkenyl, C 2-22 alkynyl, C 3-12 cycloalkyl, C 3-12 cycloalkenyl, C 7-9 aralkyl -, C3-2o-heteroalkyl, C3-i2-cycloheteroalkyl, C5-16 heteroaralkyl and A ^"represents the anion of an organic or inorganic acid, R ² and R ^{4 have} the meaning given for formula (I) and

R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently R, hydrogen, halogen, a hydroxy, amino, an optionally substituted N-mono or di-O-4-alkyl or C 2-4 hydroxyalkylamino, N-phenyl or N-naphthylamino, Ci- 28 -alkyl-, Ci- 28 -alkoxy-, phenoxy-, C2-28-alkenyl-, C2-22-alkynyl-, C3- i2-cycloalkyl, C3-i2-cycloalkenyl, C7-9-aralkyl, C3-2o-heteroalkyl, C3-12-cycloheteroalkyl, C5-i6-heteroaralkyl, phenyl or naphthyl group, wherein the substituents are selected are prepared from Ο-4-alkyl, Ο-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 Ci-6-alkyl-substituted rings connected to each other.