WO2016156351A1 - Detergent composition with improved stain removal - Google Patents

Abstract

The present invention relates to the use of a combination of water-soluble builder systems and specific acylhydrazones for improving stain removal, in particular bleachable, hydrophilic stains, such as red wine stains, tea stains, spots of red fruits or beverages and food products thereof or such products containing the corresponding dyes, of washing agents when washing textiles or cleaning hard surfaces. The invention also relates to detergents containing such a combination.

Description

 Detergent composition with improved stain removal

The present invention relates to the use of a combination of water-soluble builder systems and certain acylhydrazones to improve stain removal, especially bleachable, hydrophilic stains such as red wine stains, tea stains, red fruit stains or beverages and foods thereof, or those containing corresponding dyes, from laundry detergents Washing textiles or cleaning hard surfaces, as well as detergents containing such a combination.

Conventional bleaching agents based on active oxygen, even in the presence of stoichiometric activators (such as TAED, NOBS, DECOBS, DOBA) show good performance at use temperatures of 40 ° C and above. At low temperatures, however, the bleaching performance is limited.

The use of acylhydrazones as bleach catalyst, as described in WO 2013/104631 A1, leads to improved removal of the abovementioned stains, even at low temperatures. However, it has been found that the optimal effect depends on the interaction with other components of the formulation. Surprisingly, it has been found that the cleaning performance in formulations in which the bleach catalyst is used in combination with a water-soluble builder system is improved.

A first subject of the invention is therefore the use of a combination of a water-soluble builder system with an acylhydrazone of the general formula (I),

in the R is a CF3 or for a Ο-alkyl, C2-28 alkenyl, C2-22 alkynyl, C3-i2-cycloalkyl, C3 cycloalkenyl, phenyl, naphthyl, C7-9 aralkyl , C3-2o-heteroalkyl or C3-i2-cycloheteroalkyl, R ² and R ^{3 are} independently hydrogen or an optionally substituted C1 alkyl, C2-28 alkenyl, C2-22 alkynyl, C3-i2-cycloalkyl -, C3-i2-Cycloalkenyl-, C7-9-aralkyl, C3 heteroalkyl, C3-i2-cycloheteroalkyl, -i6-heteroaralkyl, phenyl, naphthyl or heteroaryl group or R2 and R3 together with the carbon atom connecting them for an optionally substituted 5-, 6-, 7-, 8- or 9-membered ring, which may optionally contain heteroatoms, and

R ^{4 is} hydrogen or a C 1-6 -alkyl, C 2-30 alkenyl, C 2-22 -alkynyl, C 3-12 -cycloalkyl, C 3-6 cycloalkenyl, C 7-9 -aralkyl, C 3-30 -heteroalkyl-, C3-i2-cycloheteroalkyl, Cs-i6-heteroaralkyl group or an optionally substituted phenyl or naphthyl or heteroaryl group, to increase the cleaning power of peroxygen-containing detergents.

Another object of the invention are detergents containing a peroxygen bleaching agent and a combination of water-soluble builder system and a compound of formula (I).

Yet another aspect of the invention relates to a process for washing textiles in which an agent according to the invention is used.

All amounts stated in connection with the detergents described herein are, unless stated otherwise, by weight in each case based on the total weight of the detergent. Furthermore, such amounts referring to at least one constituent always refer to the total amount of that type of constituent contained in the composition, unless explicitly stated otherwise. That is, such amounts, for example in connection with "at least one anionic surfactant", refer to the total amount of anionic surfactants contained in the middle.

"At least one," as used herein, refers to 1 or more, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or more, and does not refer to components of the compositions described herein Thus, for example, one or more different anionic surfactants, ie, at least one anionic surfactant, means, for example, one or more different anionic surfactants one or more different types of anionic surfactants. Together with quantities, the quantities refer to the total amount of the corresponding designated type of ingredient as defined above.

"Water-soluble" as used herein refers to a solubility in water at 20 ° C of at least 1 g / L, preferably at least 10 g / L.

In the context of the invention, the term cleaning power (detergency) is understood to mean the removal of one or more stains, in particular laundry stains, which are bleach-sensitive. The distance can be measured by a brightening of the soiling measured as well as assessed visually.

The detergents described herein may be detergents for textiles or natural fibers. Detergents in the context of the invention also include washing aids, which in the manual or machine textile laundry be dosed to the actual detergent to achieve a further effect or to enhance an effect. Furthermore, laundry detergents within the scope of the invention also include textile pre-treatment and post-treatment agents, ie those agents with which the laundry item is brought into contact before the actual laundry, for example for dissolving stubborn soiling, and also agents which are in a downstream of the actual textile laundry step give the laundry further desirable properties such as comfortable grip, crease resistance or low static charge. Amongst others, the fabric softeners are calculated.

The acylhydrazones of formula (I) 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 compounds according to general formula (I) include those of general formula (II),

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

_R 10 _R 10 _R o _R 10

- NO A-; -NS A-; -NI A-; ^~ NIA ^"

 \ / \ / - O - - s wears in that

R ^{10 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, C 3- 2o-heteroalkyl, C3-i2-cycloheteroalkyl, C5-i6-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 independently of one another R, hydrogen, halogen, a hydroxy, amino, an optionally substituted N-mono or di-Ci-4-alkyl or C2-4-hydroxyalkyl amino, N-phenyl or N-naphthyl-amino, C-28-alkyl, C-28-alkoxy, phenoxy, C 2-18 -alkenyl, C 2-22 -alkynyl, C 3-12 Cycloalkyl, C 3-12 cycloalkenyl, Cz-g aralkyl, C 3-30 heteroalkyl, C 3-12 cycloheteroalkyl, C 5-16 heteroaralkyl, phenyl or naphthyl, wherein the substituents are selected from Ci-4-alkyl, hydroxy, sulfo, sulfato, halogen, cyano, nitro, carboxy, phenyl, phenoxy, naphthoxy, amino, N-mono or

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.

The anion A ^" is preferably a 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 the presence of additional cations such as sodium or ammonium ions.

Particular preference is given to the acylhydrazone of the formula (III)

The performance of compounds of general formula (I) may optionally be enhanced by the presence of manganese, titanium, cobalt, nickel or copper ions, preferably Mn (II) - (II) - (IV) - (V), Cu (I) - (II) - (III), Fe (I) - (II) - (III) - (IV), Co (I) - (II) - (III), Ni (I) - (II) - (III), Ti (II) - (III) - (IV) and particularly preferably those selected from Mn (II) - (III) - (IV) - (V), Cu (I) - (II) - ( III), Fe (I) - (II) - (III) - (IV) and Co (I) - (II) - (III); If desired, the acylhydrazone can also be used in the form of complex compounds of said metal central atoms with ligands of general formula (I) and in particular of general formula (II). A bleach-enhancing complex which has a ligand with a skeleton of the formula (I) may have the corresponding ligand once or more than once, in particular twice. It may be one or possibly two or more nuclear. 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 Ci-ie-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.

The water-soluble builder systems serve to soften water, enhance detergency, grayness inhibition and soil dispersion. Since phosphorus and / or nitrogen-containing builders have come under criticism as detergent components for ecological reasons, water-insoluble aluminosilicates, in particular zeolite, have nowadays become established on a large scale, especially in textile detergent formulations. Together with these are often polymeric polycarboxylates, in particular copolymers based on acrylic acid and maleic acid having molecular weights in the range of 20,000 to 100,000 g / mol, used together with soda and complexing agents. However, it has now surprisingly been found that the acylhydrazone-based bleach catalysts described above provide enhanced bleach performance and therefore improved stain removal of the detergent when used with water-soluble builder systems in place of the water-insoluble zeolites. Particularly high bleaching performance is unexpectedly obtained when using soluble builder systems that are substantially free of aluminosilicate, especially zeolite, alkali citrate, and aminoalkane phosphonate, especially DTPMP.

The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular glycinediacetic acid, methylglycinediacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamine-N, N'-disuccinic acid and Hydroxyiminodisuccinate, ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular Aminotris (methylenphosphonsäure ), Ethylenediaminetetrakis (methylenephosphonic acid), lysine tetra (methylenephosphonic acid) and 1-hydroxyethane-1, 1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, especially by oxidation of polysaccharides accessible polycarboxylates, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers from these, which may also contain copolymerized small amounts of polymerizable substances without carboxylic acid functionality. The relative average molecular weight (here and hereinafter: weight average) of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g / mol and 200,000 g / mol, that of the copolymers between 2,000 g / mol and 200,000 g / mol, preferably 50 000 g / mol to 120 000 g / mol, in each case based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative average molecular weight of 50,000 to 100,000. Suitable, although 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. is. As water-soluble organic builders, it is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer. 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. The third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol. In particular, preferred are vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example of C 1 -C 4 -carboxylic acids, with vinyl alcohol. Preferred polymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleinate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate. Very particular preference is given to polymers in which the weight ratio of (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2 , 5: 1 lies. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt may also be a derivative of an allylsulfonic acid substituted in the 2-position with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives is. Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, from 10% by weight to 30% by weight. %, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or methallyl sulfonate and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a carbohydrate , This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred. Particularly preferred is sucrose. The use of the third monomer presumably incorporates predetermined breaking points into the polymer which are responsible for the good biodegradability of the polymer. These terpolymers generally have a relative average molecular weight between 1,000 g / mol and 200,000 g / mol, preferably between 200 g / mol and 50,000 g / mol. Further preferred copolymers are those which contain acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts. Such organic builders may be included in amounts of up to 40% by weight, more preferably up to 25% by weight and even more preferably up to 8% by weight. In various embodiments, it may further be preferred for the amount of alkali citrate to be at most 5% by weight, preferably at most 0.5% by weight, very preferably 0% by weight. In addition to or as an alternative to the above, other water-soluble inorganic builder materials may be included. In addition to the polyphosphates, such as sodium triphosphate, these include in particular the water-soluble crystalline and / or amorphous alkali metal silicate builders. Such water-soluble inorganic builder materials are preferably present in the compositions in amounts of from 1% to 20% by weight, in particular from 5% to 15% by weight. The alkali metal silicates useful as builder materials preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1, 1 to 1: 12, and may be amorphous or crystalline. 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 .beta.- and .delta.-sodium disilicates (Na.sub.2Si.sub.20.sub.y H.sub.2O) are preferred. Also prepared from amorphous alkali silicates, practically anhydrous crystalline alkali metal silicates of the above general formula in which x is a number from 1, 9 to 2, 1, can be used in the compositions. 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. Sodium silicates with a modulus in the range of 1.9 to 3.5 are used in another embodiment. In a preferred embodiment of such agents, a granular compound of alkali silicate and alkali carbonate is used, as it is commercially available, for example, under the name Nabion® 15.

In various preferred embodiments, the soluble builder system consists of a) an alkali silicate having a modulus M20: SiO 2, where M is an alkali metal ion, in the range of 1: 1, 9 to 1: 3.3, b) an alkali carbonate, c) a polymeric polycarboxylate having a molecular weight of less than 10,000 g / mol, and d) a phosphonate capable of complex formation, and e) optionally an acid-acting component. Typically, the soluble builder system constitutes less than 40% by weight of the total composition and the alkali product of the compositions is in the range of 7.0 to 1.1.

The alkali product is a quantity that allows statements about the alkalinity of detergents. To determine the alkali product, a pH titration of a 10 wt .-% solution of the agent in water with a pH electrode and 1, 0 molar hydrochloric acid is performed. The alkali product is calculated as follows: Alkali product = 1 · initial pH

 E - 6

 V: consumption of 1.0 molar HCl at pH

 E: weight in g

 Initial pH: pH of the 10% by weight solution

If the alkali product is more than 10, it allows statements about the initial pH as well as about the buffering capacity of the solution; if it is at or below 10, then it is identical to the initial pH, statements about the buffer behavior of the solution are then not possible from the size.

The alkali product of the agents according to the invention is in the range from 7.0 to 1.1. Preferably, it is in the range of 8.5 to 11, 2, the agents in an especially preferred embodiment of the invention having an alkali product of 10.7 + 0.4.

In this case, the alkali product of the agent is determined by the composition according to the invention and can be specifically influenced in particular with the aid of the acid-acting component. For this purpose, all suitable for use in detergents acidic components are. These may be both carboxylic acids and mineral acids or acid salts of mineral acids. Among the carboxylic acids, in particular those are preferred which are also suitable as co-builders. Here are in particular polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for environmental reasons, as well as mixtures of these. These acids can be used anhydrous or in the form of their hydrates. Among the usable mineral acids are in particular sulfuric acid, phosphoric acid, carbonic acid and hydrochloric acid, and their acid salts, to call. Citric acid and / or sodium hydrogen sulfate are preferably used in the compositions according to the invention as acidic components, the sole use of citric acid being a particularly advantageous embodiment. However, the content of the agent on the acidic component is preferably not more than 10.0% by weight; in particularly preferred embodiments, it is in the range 0, 1 and 5 wt .-%. In this case, the acidic component can in principle be added at any stage of preparation of the agent. However, it is preferred if the acid-acting component is added to the detergent subsequently, wherein the acid-acting component is present either alone or in the form of compounds with other, preferably neutral-reacting, detergent ingredients.

Essential for the alkali product is further the total content of builder substances. It should not be more than 40% by weight in the compositions according to the invention, in a preferred embodiment of the invention being in the range from 20 to 35% by weight. Especially low Levels of builder substances are possible when the active in the wash liquor alkali carbonate is not predominantly via the direct entry of alkali carbonate, such as soda, but when the alkali carbonate of precursors that form only during the process alkali carbonate, is provided. Particularly noteworthy here is alkali metal percarbonate, which liberates alkali carbonate under the influence of moisture. In this case, for example, the sodium percarbonate preferably used as a bleach in the wash liquor provides 68% of its weight as soda. If sodium percarbonate is used as the bleach, it provides at least 30% by weight of the total alkali carbonate active in the wash liquor, preferably even more than 50% by weight. Nevertheless, according to the invention, sodium percarbonate is not expected to be the soluble builder system since it is primarily a bleaching agent. Accordingly, in compositions containing sodium percarbonate as a bleaching agent, particularly low levels of the soluble builder system can be adjusted without detriment to washing properties. Such agents preferably contain only 10 to 25% by weight of the soluble builder.

The alkali carbonates used in the builder system are preferably sodium and / or potassium carbonate, with the use of sodium carbonate in particular being preferred. The content of these alkali metal carbonates is preferably chosen so that the content of active in the wash liquor alkali carbonate 10 to 30 wt .-%, particularly preferably 15 to 25 wt .-%, of the total composition.

The alkali metal silicates used in this system are, in preferred embodiments according to the invention, amorphous sodium silicates having a modulus Na 2 O: SiO 2 of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are delay-delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays which have a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray-amorphous silicates, which likewise have a dissolution delay compared with the conventional water glasses, are described, for example, in German patent application DE-A-4400024. Especially preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates. Granular amorphous alkali metal silicates having bulk densities of at least 700 g / l can be prepared, for example, by a process described in the patent application WO 97/34977, which starts from the spray-drying and includes the compression of the spray-dried bead. In this case, the spray-dried bead is ground and at the same time or subsequently granulated with the addition of a liquid granulation assistant, bulk densities of at least 700 g / l - up to above 1000 g / l - being set.

In particular, the alkali silicates according to the invention can also be used in preparation forms in which they are present together with alkali carbonate.

In a further embodiment of the invention, crystalline, layered sodium silicates of the general formula Na 2 SixO 2 x + 1 yH 2 O wherein x is 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. Such crystalline sheet silicates are described, for example, in European Patent Application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates

Na2Si205'yH20 is preferred.

Regardless of which alkali metal silicate is used, the total content of alkali metal silicate in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

The polymeric polycarboxylates are preferably homopolymers or copolymers which contain acrylic acid and / or maleic acid units. For the purposes of the present invention, homopolymers are particularly preferably used, again polyacrylates being preferred. Usually, the polyacrylates are used in the form of sodium salts. In particular, polyacrylates which preferably have a molecular weight of from 3,000 to 8,000 and more preferably from 4,000 to 5,000 g / mol have proven to be particularly suitable according to the invention. The molecular weights indicated in this specification for polymeric polycarboxylates are weight-average molar masses M _w , which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally higher than the molecular weights specified in this document. These polymeric polycarboxylates are in the agent preferably in amounts of 0.5 to 8 wt .-%, in particular from 2 to 6.5 wt .-%, included.

In addition to the polycarboxylates essential to the invention with molar masses of not more than 10,000 g / mol, the copolymers may also contain the copolymeric polycarboxylates usually used as co-builders, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid, having a molecular weight of between 20,000 and 70,000 g / mol. Copolymers of acrylic acid with maleic acid, which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid, have proved to be particularly suitable. To improve the water solubility, the polymers may also contain allylsulfonic acids, such as in EP-B-727448 allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer. Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those which, according to DE-A-43 00 772, as monomers, salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 contain as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives. Further preferred copolymers are those which are described in the German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate. In a preferred variant, both these copolymers and the polyacrylates essential to the invention are used in the process, wherein the ratio of the polyacrylate to the acrylic acid-maleic acid copolymer in the range 2: 1 to 1: 20, preferably 1: 1 to 1: 15 , lies. However, the content of such long-chain polycarboxylates in the compositions is at most 5 wt .-%. In another, likewise preferred embodiment of the invention, the agents contain, in addition to the polymeric polycarboxylate having a molecular weight of less than 10,000 g / mol, no further polymer of acrylic acid, in particular no copolymer of acrylic acid with maleic acid.

Another component of the builder system are phosphonates. These are in particular hydroxyalkanephosphonates. Among the hydroxyalkane phosphonates, the 1-hydroxyethane-1, 1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Although it is also possible to use aminoalkanephosphonates, such as ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs, these preferably being in the form of the neutrally reacting sodium salts, eg. For example, as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP, the agents described herein in preferred embodiments are free of aminoalkane phosphonates, particularly free of DTPMP "free of" as used in this context in that the content is less than 2 Wt .-%, preferably less than 1 wt .-%, more preferably less than 0, 1 wt .-%, most preferably 0 wt .-% based on the agent. As a builder, HEDP is preferably used from the class of phosphonates. Such phosphonates are usually included in the compositions in amounts of 0.05 to 2.0 wt .-%, preferably in amounts of 0, 1 to 1, 5 wt .-%.

In various embodiments, the detergents contain substantially no aluminosilicate. "Essentially no aluminosilicate" means that the content of aluminosilicates, in particular zeolite, is less than 5% by weight, based on the agent, preferably less than 3% by weight, more preferably less than 1% by weight, most preferably less than or equal to 0. If aluminosilicates are included, it is not because of their water softening effect or their carrier function that they can be present only if they are used as granulating aids, for example for powdering.

In some embodiments, the detergent is characterized in that a) it contains bleach activators in amounts of up to 10 wt.%, In particular from 1.5 wt.% To 5 wt.%, And / or b) the content Aluminosilicates, in particular zeolite, less than 5% by weight, preferably less than 3% by weight, more preferably less than 1% by weight, most preferably less than 0.5% by weight, and / or c) the maximum amount of alkali citrate 5% by weight, preferably at most 0.5% by weight, very preferably 0% by weight, and / or d) the content of aminoalkane phosphonates, in particular of DTPMP, less than 2% by weight, preferably less than 1% by weight %, more preferably less than 0.1% by weight, most preferably 0% by weight, based on the agent.

It is particularly preferred if the detergent is characterized in that the content of aluminosilicates, in particular zeolite, less than 5 wt .-%, preferably less than 3 wt .-%, more preferably less than 1 wt .-%, most preferably less than 0.5 wt % and c) the amount of alkali citrate is at most 5% by weight, preferably at most 0.5% by weight, very preferably 0% by weight and d) the content of aminoalkane phosphonates, in particular of DTPMP, is less than 2 % By weight, preferably less than 1% by weight, more preferably less than 0.1% by weight, most preferably 0% by weight, based on the agent.

Most preferably, the detergent is characterized in that a) it contains bleach activators in amounts of up to 10 wt .-%, in particular from 1, 5 wt .-% to 5 wt .-% and b) the content of aluminosilicates, in particular Zeolite, less than 5% by weight, preferably less than 3% by weight, more preferably less than 1% by weight, most preferably less than 0.5% by weight and c) the amount of alkali citrate is not more than 5% by weight, preferably at most 0.5% by weight, more preferably 0% by weight and d) the content of aminoalkane phosphonates, in particular DTPMP, less than 2% by weight, preferably less than 1% by weight, more preferably less than 0, 1 wt .-%, most preferably 0 wt .-% based on the agent. In the context of the use according to the invention, it is preferred if the concentration of the compound according to formula (I) in aqueous liquor, as used for example in washing machines or dishwashers, 0.5 μιηοΙ / Ι to 500 μιηοΙ / Ι, in particular 5 μιηοΙ / Ι to 100 μιηοΙ / Ι amounts. The above-mentioned complex-forming metal ions are preferably not intentionally added, but they may be present from possible sources of such metal ions, which include, in particular, the tap water, the washing machine itself, adhesions to textiles, and stains on the fabrics. Optionally, metal ions inadvertently introduced with other detergent ingredients may also be considered. Preferred peroxygen concentrations (calculated as H2O2) in the 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 40 ° C., and particularly preferably at temperatures below 30 ° C. The water hardness of the water used for preparing the aqueous liquor is preferably in the range from 0 ° dH to 21 ° dH, in particular 0 ° dH to 3 ° 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. The use 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.

Because of the low builder content, in particular in relation to the possible surfactant content, the agents can also be metered low in the washing process. Thus, it is preferred if the agent is metered so that a maximum of 45 g, preferably between 10 and 35 g, of the soluble builder system are used during the wash cycle in a household washing machine. It is ensured by the amounts of builder contained in the wash liquor that the builders perceive a sufficient water softening function. In this case, the builder system can preferably be metered largely independently of the water hardness. However, in the case of large water hardnesses, it may be preferable for builder amounts in the upper half of the stated range of from 20 to 45 g, in particular from 25 to 35 g, to be metered in the wash cycle.

The use according to the invention is preferably carried out by allowing a peroxygen compound and a detergent containing an acylhydrazone of the general formula (I) and a water-soluble builder system to act on a contaminated textile in the course of a machine or hand washing operation. The use according to the invention can be particularly easily achieved by the use of a detergent, the peroxygen compound, water-soluble builder system and a compound of formula (I) or a containing by complexing with a said transition metal ion from this accessible bleach catalyst, be realized in the laundry of textiles requiring cleaning. Alternatively, the peroxygen compound and / or the compound of formula (I) and / or a complex obtainable therefrom and / or the water-soluble builder system can also be added separately to a wash liquor which has a detergent without the particular ingredient mentioned.

Another object of the invention is a detergent containing a peroxygen bleaching agent and a combination of water-soluble builder system and a compound of formula (I).

In the context of use preferred embodiments also apply to the category of detergents; in particular, the compound of formula (I) may also be present in the form of a bleach catalyst obtainable by complexation with a transition metal ion thereof from said agent.

Preferably in detergents 0.001 wt .-% to 5 wt .-%, in particular 0.05 wt .-% to 0.15 wt .-% and particularly preferably 0.03 wt .-% to 0.09 wt .-% the compound according to formula (I). In particular, when a compound of the formula (I) is present, it is 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 a compound according to formula (I). Then, the molar ratio of said transition metal or the sum of said transition metals to the compound according to formula (I) 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 Agents are contained in these 0.05 wt .-% to 1 wt .-%, in particular 0.1 wt .-% to 0.5 wt .-% of bleach-enhancing complex having a ligand according to formula (I) included. Preferred transition metal is Mn.

As peroxygen compounds contained in the agents are in particular organic peracids or pers acid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperoxododecanedioic acid, other peroxo acids or peroxyacid salts, such as alkali metal or peroxodisulfates or caroates, or diacyl peroxides or tetraacyldiperoxides, hydrogen peroxide and under the washing conditions, hydrogen peroxide-releasing substances, such as alkali metal perborates, alkali metal peroxides, alkali metal peracidates and urea perhydrate, into consideration. 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. Especially preferred is alkali metal percarbonate, alkali metal perborate monohydrate, alkali metal perborate tetrahydrate or hydrogen peroxide in the form of aqueous solutions containing 3 wt .-% to 10 wt .-% hydrogen peroxide used. Preferably, peroxygen compounds are present in the compositions in amounts of up to 50% by weight, more preferably from 2% to 45% and more preferably from 5% to 20% by weight.

In a further preferred embodiment of the invention, in particular in the presence of H2O2 releasing peroxygen compound, a conventional bleach activator is used together with the acyl hydrazone of the general formula (I), the general formula (II) and in particular the formula (III). In detergents such bleach activators are preferably present in amounts of up to 10 wt .-%, in particular from 1, 5 wt .-% to 5 wt .-%. Preference is given to using peroxycarboxylic acid-forming compound and acylhydrazone in molar ratios in the range from 4: 1 to 100: 1, in particular from 25: 1 to 50: 1, under perhydrolysis conditions.

Compounds which can be added under perhydrolysis conditions to give peroxocarboxylic acid are, in particular, compounds which, under perhydrolysis conditions, optionally substituted perbenzoic acid and / or aliphatic peroxycarboxylic acids having 1 to 12 C atoms, in particular 2 to 4 C atoms, are used alone or in mixtures. Suitable are bleach activators which carry O- and / or N-acyl groups, in particular of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to 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 ), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates or carboxylates or the sulfonic or carboxylic acids of these, in particular nonanoyl or isononanoyl or lauroylbenzenesulfonate (NOBS or iso-NOBS or LOBS) or decanoyloxybenzoate (DOBA) whose formal carbonic acid ester derivatives such as 4- (2-decanoyloxyethoxycarbonyloxy) benzenesulfonate (DECOBS), acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and acetylated sorbitol and mannitol and mixtures thereof (SORMAN), acylated sugar derivatives, especially pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetyl xylose and octaacetyl lactose, acety lated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N- benzoylcaprolactam.

In addition to or as an alternative to the compounds which form peroxycarboxylic acids under perhydrolysis conditions, further bleach-activating compounds, such as, for example, nitriles, from which perimides acids are formed under perhydrolysis conditions, may be present. These include in particular aminoacetonitrile derivatives with quaternized nitrogen atom according to the formula

R ¹¹

 I

R ² -N ( ⁺ ) - (CR ⁴ R ⁵ ) -CN X (-)

 I

_R 13

in the R represents -H, -CH3, a C2-24-alkyl or alkenyl radical, a substituted Ci-24-alkyl or C2-24-alkenyl radical having at least one substituent from the group -Cl, -Br, -OH , -NH2, -CN and -N ⁽⁺⁾ - CH2-CN, an alkyl or alkenylaryl radical having a Ο-24-alkyl group, or a substituted alkyl or alkenylaryl radical having at least one, preferably two, optionally substituted Ci-24 -Alkyl group (s) and optionally further substituents on the aromatic ring, R ² and R ^{3 are} independently selected from -CH 2 -N-CN, -CH ₃ , -CH 2 -CH ₃ , -CH 2 -CH 2 -CH ₃ , -CH (CH ₃ ) -CH _3, -CH ₂ -OH, -CH 2 -CH 2 OH, -CH (OH) _-CH3, -CH2-CH2-CH2-OH, -CH ₂ -CH (OH) -CH _3, -CH ( OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) n H where n = 1, 2, 3, 4, 5 or 6, R ⁴ and R ⁵ independently of one another are above for R, R ² or R ³ have meaning given, wherein at least 2 of said radicals, in particular R ² and R ³ , including the inclusion of the nitrogen atom and optionally further heteroatoms can be linked to one another in a ring-closing manner and then preferably form a morpholino ring, and X is a charge-balancing anion, preferably selected from benzenesulfonate, toluenesulfonate, cumene sulfonate, the C9 -15-alkylbenzenesulfonates, the C-20-alkyl sulfates, the Cs; 22-Carbonsäure- methyl ester sulfonates, sulfate, hydrogen sulfate and mixtures thereof, can be used. Oxygen-carrying sulfonimines can also be used.

To avoid interaction with the peroxygen compounds, the bleach activators may have been coated or granulated in known manner with coating substances, granulated tetraacetylethylenediamine having average particle sizes of 0.01 mm to 0.8 mm, granulated by means of carboxymethylcellulose 1, 5-diacetyl-2,4-dioxo-hexahydro-1, 3,5-triazine, and / or formulated in particulate form Trialkylammoniumacetonitrile is particularly preferred.

In addition to the combination to be used according to the invention, it is also possible to use customary bleach-activating transition metal complexes. These are preferably selected from the cobalt, iron, copper, titanium, vanadium, manganese and ruthenium complexes. Suitable ligands in such transition metal complexes are both inorganic and organic compounds, which in addition to carboxylates in particular compounds having primary, secondary and / or tertiary amine and / or alcohol functions, such as pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole , triazole, 2,2 ^{'-bispyridylamine,} tris (2- pyridylmethyl) amine, 1, 4,7-triazacyclononane and its substituted derivatives such as 1, 4,7-trimethyl-1, 4,7-triazacyclononane, 1, 5,9-triazacyclododecane and its substituted derivatives such as 1, 5,9- Trimethyl-1, 5,9-triazacyclododecane 1, 4,8,1,1-tetraazacyclotetradecane and its substituted derivatives such as 5,5J, 12,12,14-hexamethyl-1,4,8,1-tetraazacyclotetradecane, 1 , 5,8,12-Tetraazabicyclo [6.6.2] hexadecane and its substituted derivatives, such as 5,12-diethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane, (bis ((( 1-methylimidazol-2-yl) -methyl)) - (2-pyridylmethyl) -amine, N, N ^' - (bis (1-methylimidazol-2-yl) -methyl) -ethylenediamine, N-bis- (2 -benzimidazolylmethyl) aminoethanol, 2,6-bis (bis (2-benzimidazolylmethyl) aminomethyl) -4-methylphenol, N, N, N ^{', N'} tetrakis- (2-benzimidazolylmethyl) -2-hydroxy -1, 3-diaminopropane, 2,6-bis (bis (2-pyridylmethyl) aminomethyl) -4-methylphenol, 1, 3-bis (bis (2-benzimidazolylmethyl) aminomethyl) benzene, sorbitol, mannitol , Erythritol, adonitol, inositol, Lactose, and optionally substituted salene, porphins and porphyrins. The inorganic neutral ligands include in particular ammonia and water. If not all coordination sites of the transition metal central atom are occupied by neutral ligands, the complex contains further, preferably anionic and among these in particular mono- or bidentate ligands. These include in particular the halides such as fluoride, chloride, bromide and iodide, and the (NO 2) ^- group, that is a nitro ligand or a nitrito ligand. The (NO 2) ^- group may also be chelated to a transition metal or it may be asymmetric or two transition metal atoms -0-bridging. In addition to the ligands mentioned, the transition metal complexes may carry further, generally simpler ligands, in particular mono- or polyvalent anion ligands. In question, for example, nitrate, acetate, trifluoroacetate, formate, carbonate, citrate, oxalate, perchlorate and complex anions such as hexafluorophosphate. The anion ligands should provide charge balance between the transition metal central atom and the ligand system. The presence of oxo ligands, peroxo ligands and imino ligands is also possible. In particular, such ligands can also act bridging, so that polynuclear complexes arise. In the case of bridged, dinuclear complexes, both metal atoms in the complex need not be the same. The use of binuclear complexes in which the two transition metal central atoms have different oxidation numbers is also possible. If anion ligands are missing or the presence of anionic ligands does not result in charge balance in the complex, anionic counterions which neutralize the cationic transition metal complex are present in the transition metal complex compounds to be used according to the invention. These anionic counterions include in particular nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate, perchlorate, the halides such as chloride or the anions of carboxylic acids such as formate, acetate, oxalate, benzoate or citrate. Examples of usable transition metal complex compounds are Μη (ΐν) 2 (μ-O) 3 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) di-hexafluorophosphate, [N, N'-bis [(2 -hydroxy-5-vinylphenyl) -methylene] -1,2-diaminocyclohexane] -manganese (III) chloride, [Ν, Ν'-bis [(2-hydroxy-5-nitrophenyl) methylene] -1, 2 diaminocyclohexane] manganese (III) acetate, [N, N'-bis [(2-hydroxyphenyl) methylene] -1, 2-phenylenediamine] manganese (III) acetate, [N, N'- bis [(2-hydroxyphenyl) - methylene] -1,2-diaminocyclohexane] manganese (III) chloride, [N, N'-bis [(2-hydroxyphenyl) methylene] -1, 2-diaminoethane] manganese (III) chloride, [N, N'-Bis [(2-hydroxy-5-sulfonatophenyl) -methylene] -1,2-diaminoethane] manganese (III) chloride, manganese oxalato complexes, nitropentammine cobalt (III) chloride , Nitritopentammine cobalt (III) chloride, hexammine cobalt (III) chloride, chloropentammine cobalt (III) chloride, and the peroxo complex [(NH3) 5Co-0-0-Co (NH3) 5] Cu.

The water-soluble builder systems are included in the compositions of the invention in the amounts disclosed above within the scope of the use.

Detergents, which may be in the form of homogeneous solutions or suspensions, especially in powdered solids, in densified particle form, can in principle all known and known except for the invention to be used combination of water-soluble builder system and compound of formula (I) and optionally the said bleach activators and catalysts contain usual ingredients in such agents. The agents may, in particular, be surface-active surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, special effect polymers such as soil release polymers, dye transfer inhibitors, grayness inhibitors, wrinkle-reducing polymeric agents and form-retaining polymeric agents, and other adjuvants such as optical brighteners , Foam regulators, dyes and fragrances.

An agent may be used to further enhance the disinfecting effect, for example against specific germs, in addition conventional antimicrobial agents such as alcohols, aldehydes, acids, carboxylic acid esters, acid amides, phenols and phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, bound to organic frameworks O-acetates and O. -Formals, benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, amines, quaternary ammonium compounds, guanidines, amphoteric compounds, quinolines, benzimidazoles, IPBC, dithiocarbamates, metals and metal compounds such as silver and silver salts, halogens such as chlorine, iodine and theirs Compounds, other oxidizing agents and inorganic nitrogen compounds. Such antimicrobial additives are preferably present in amounts of up to 10 wt .-%, in particular from 0.01 wt .-% to 5 wt .-%, each based on the total agent included; in a preferred embodiment, however, they are free of such additional disinfecting agents.

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. As anionic surfactants, for example, those of the sulfonate type and sulfates are used. Preferred surfactants of the sulfonate type are C9-i3-alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C12 -18 monoolefins having terminal or internal double bonds by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates, which are obtained from C12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise suitable are the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Suitable alkylbenzenesulfonates are preferably selected from linear or branched alkylbenzenesulfonates of the formula

in which R ^' and R ^"are independently H or alkyl and together contain from 6 to 19, preferably from 7 to 15, and in particular from 9 to 13, carbon atoms A particularly preferred representative is sodium dodecylbenzylsulfonate.

Alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12-18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those monoesters secondary Alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the Ci2-Ci6-alkyl sulfates and Ci2-Ci5-alkyl sulfates and C14-C15-alkyl sulfates are preferred.

Also, the sulfuric acid monoesters of straight-chain or branched C7-2i alcohols ethoxylated with from 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C9-11 alcohols having on average 3.5 moles of ethylene oxide (EO) or C12-C18 fatty alcohols with 1 up to 4 EO, are suitable. Suitable alkyl ether sulfates are, for example, compounds of the formula

R -O- (AO) _n -SO ₃ - X ⁺ In this formula, R 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 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with even number of carbon atoms are preferred. Particularly preferred radicals R are derived from C 12-18 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 index n stands for an integer from 1 to 50, preferably from 1 to 20 and especially from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7 or 8. X stands for a monovalent cation or the nth part of an n-valent cation, the alkali metal ions are preferred, and Na ⁺ or K ⁺ including Na, with Na ^{+ being} extremely preferred. Other cations X + can be selected from NhV,

Mn ²⁺ , and mixtures thereof.

In various embodiments, the alkyl ether sulfate may be selected from fatty alcohol ether sulfates of the formula

with k = 1 1 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are Na-Ci2-14 fatty alcohol ether sulfates with 2 EO (k = 1 1-13, n = 2 in Formula A-1). The stated degree of ethoxylation represents a statistical average that may be an integer or a fractional number for a particular product. The indicated degrees of alkoxylation represent statistical averages, which may be an integer or a fractional number for a particular product. Preferred alkoxylates / ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).

As further anionic surfactants are particularly soaps into consideration. Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants, including the soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium, potassium or magnesium salts, in particular in the form of the sodium salts. In the selection of anionic surfactants are the freedom from formulation no conditions to be observed in the way. Preferred anionic surfactants to be used are the alkylbenzenesulfonates and fatty alcohol sulfates, in particular the alkylbenzenesulfonates.

Anionic surfactants including the soaps, i. in particular alkylbenzenesulfonates, alkyl ether sulfates and soaps, are preferably present in the detergent at a certain proportion by weight, namely from 5 to 25% by weight, based on the total weight of the detergent formulation. Preference is given to amounts of from 7 to 20% by weight of anionic surfactants, based on the total weight of the detergent formulation. Regardless of whether the detergent contains one or more of the anionic surfactants, the amounts given refer to the total amount of all anionic surfactants contained in the detergent.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates having linear radicals of alcohols of native origin having 12 to 18 carbon atoms, e.g. from coconut, palm, tallow or oleyl alcohol, and on average from 2 to 8 EO per mole of alcohol. The preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 7 -n-alcohol with 7 EO, cis-is alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-14 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.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.

Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG). Usable alkylpolyglycosides satisfy the general formula RO (G) _z , in which R is a linear or branched, especially in the 2-position methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The glycosidation degree z is between 1, 0 and 4.0, preferably between 1, 0 and 2.0 and in particular between 1, 1 and 1, 4. Preference is given to using linear alkyl polyglycosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

Such surfactants are present in detergents in proportions of preferably from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight.

Suitable enzymes in the detergents are, in particular, those from the class of proteases, cutinases, amylases, lipases, pullulanases, xylanases, hemicellulases, cellulases, peroxidases and oxidases or mixtures thereof, the use of protease, amylase, lipases and / or or cellulase is particularly preferred. The proportion is preferably 0.2 wt .-% to 1, 5 wt .-%, in particular 0.5 wt .-% to 1 wt .-%. The enzymes can be adsorbed in a customary manner on carriers and / or embedded in coating substances or incorporated as concentrated, as anhydrous liquid formulations.

Suitable gravel inhibitors or soil release agents are cellulose ethers, such as carboxymethylcellulose, methylcellulose, hydroxyalkylcelluloses and cellulose mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose and methylcarboxymethylcellulose. Preferably, sodium carboxymethylcellulose and mixtures thereof with methylcellulose are used. Commonly used soil release agents include copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. The proportion of graying inhibitors and / or soil-release active ingredients in the compositions is generally not more than 2% by weight and is preferably from 0.5% by weight to 1.5% by weight.

As optical brighteners for particular textiles made of cellulose fibers (for example cotton), detergents may contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazin-6-yl-amino) -stilbene-2,2'-disulphonic acid or similarly constructed compounds which are suitable instead of the morpholino group, carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group. Furthermore, brighteners of the type substituted 4,4'-distyryl-diphenyl, for example 4,4'-bis- (4-chloro-3-sulfostyryl) -diphenyl. Also, mixtures of brighteners can be used. For polyamide fibers are particularly well brighteners of the type of 1, 3-diaryl-2-pyrazolines, for example 1- (p-sulfoamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline and similarly structured compounds. The content of the composition in optical brighteners or brightener mixtures is generally not more than 1 wt .-%, and preferably in the range of 0.05 wt .-% to 0.5 wt .-%.

The customary foam regulators which can be used in detergents include, for example, polysiloxane-silica mixtures, the finely divided silica contained therein preferably being silanated or otherwise rendered hydrophobic. The polysiloxanes can consist of both linear compounds as well as crosslinked polysiloxane resins and mixtures thereof. Further antifoams are paraffin hydrocarbons, in particular microparaffins and paraffin waxes whose melting point is above 40 ° C., saturated fatty acids or soaps having in particular 20 to 22 carbon atoms, for example sodium behenate, and alkali metal salts of phosphoric mono- and / or dialkyl esters in which the alkyl chains each having 12 to 22 carbon atoms. Among these, preference is given to using sodium monoalkyl phosphate and / or dialkyl phosphate having C 16- to C 18 -alkyl groups. The proportion of foam regulators may preferably be from 0.2% by weight to 2% 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 alkali metal hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are preferably not more than 10 wt .-%, in particular from 0.5 wt .-% to 6 wt .-%, included.

Any of the detergents described herein may be any method known in the art. The preparation of solid compositions can be carried out in a manner known in principle, for example by spray-drying or granulation, with thermally sensitive ingredients optionally being added separately later.

The compositions are preferably in the form of pulverulent, granular or tablet-like preparations which are prepared in a manner known per se, for example by mixing, granulating, roller compacting and / or spray-drying the thermally stable components and admixing the more sensitive components, in particular enzymes, bleaches and bleach-activating agents Active ingredients are expected to be produced. For the production of funds with increased bulk density, in particular in the range of 650 g / l to 950 g / l, a process comprising an extrusion step is preferred.

For the preparation of agents in tablet form, the procedure is preferably such that all components are mixed together in a mixer and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, with pressing pressures in the range of 200 10 ⁵ Pa to 1 500 10 ⁵ Pa pressed. This gives unbreakable, yet sufficiently rapidly soluble tablets under application conditions with flexural strength of usually over 150 N. Preferably, a tablet thus produced has a weight of 15 g to 40 g, in particular from 20 g to 30 g, with a diameter of 35 mm to 40 mm.

Another object of the invention is a method for washing textiles in which an agent according to the invention is used. This agent is preferably metered so that during the wash cycle in a household washing machine a maximum of 45 g, preferably between 10 and 35 g, of the soluble builder system are used. In this case, the builder system can preferably be metered largely independently of the water hardness. However, in the case of large water hardnesses, it may be preferable for builder amounts in the upper half of the stated range of from 20 to 45 g, in particular from 25 to 35 g, to be metered in the wash cycle. Washing process, i. In particular, processes for cleaning textiles are generally distinguished by the fact that cleaning-active substances are applied to the items to be cleaned in one or more process steps and washed off after the action time, or that the items to be cleaned are otherwise treated with a detergent or a solution of this agent.

In the described washing processes, in various embodiments of the invention, temperatures of up to 95 ° C or less, 90 ° C or less, 60 ° C or less, 50 ° C or less, 40 ° C or less, 30 ° C or less, or 20 ° C or less used. These temperature data refer to the temperatures used in the washing steps.

In various embodiments, the uses, compositions and methods described above in connection with detergents are also applicable to hard surface cleaners. The invention thus also encompasses the use of the described combinations for improving the cleaning performance of hard surface cleaners, corresponding cleaning agents and methods in which such cleaners are used. Furthermore, all facts, objects and embodiments described for the uses and detergents are also applicable to the washing processes and vice versa.

Examples

Example 1: Detergent formulations

 Table 1 shows a powder detergent B according to the invention in comparison with a powder detergent A not according to the invention (all data in% by weight, unless stated otherwise):

Table 1: Detergent compositions

) Morpholinium 4- (2- (2 - ((2-hydroxyphenylmethyl) methylene) hydrazinyl) -2-oxoethyl) -4-methyl chloride The measured pH in the wash liquor is 8.9 for Formula A and 9.8 for Formula B. Example 2: Washing tests

 For the washing tests, household washing machines (Miele W 1935) were loaded with 3.5 kg accompanying laundry as well as the soiled cloth rags (cotton). In addition, 74 g / 100 ml of the detergent to be tested were added and washed at 20 ° C. It was detergent A from Table 1 used as a reference and compared with the detergent B according to the invention, After hanging drying and mangling of the cloth rags their whiteness was determined spectrophotometrically (Minolta CR200-1).

The values given (Table 2) are mean values of 6 determinations. The soiled textiles were bought or self-made. The differences between the remission values and the standard detergent are shown. The use of the acylhydrazone bleach catalyst in the soluble builder-based detergent formulation B, as compared to the zeolite and DTPMP based detergent formulation A, exhibits improvements in leachability, particularly on bleachable soils.

Table 2: Washer

 Soil Origin / Species Diff. B against A

 Coffee CFT BC2 0,7

 Tea (low temp.) CFT BC3 3.8

 Red wine, fresh CFT CS103 2,6

 Black currant CFT CS12 4.2

 Blueberry juice CFT CS15 5, 1

 Red wine Equest Redwine 3.0

 Blueberry juice Rabenhorst 8.9

 Red wine Bordeaux 3,4

 Tea Messner, Assam Ceylon 10 3.2

 Tea (high / middle temp.) CFT BC1 3.2

 Red wine, aged CFT CS03 2,7

 Tea EMPA 167 7.2

 Black currant juice WFK 10JB 2.1

 Curry WFK 10U 0.4

 Blueberry juice WFK 10WB 1, 2

 Blood EMPA 1 1 1 18.5

Claims

 claims

1. Use of a combination of a soluble builder system with an acylhydrazone of the general formula (I),

 in the R represents a CF 3 or represents a Ο-28-alkyl, C 2-18 alkenyl, C 2-22 alkynyl, C 3-12 cycloalkyl, C 3-12 cycloalkenyl, phenyl, naphthyl, C7-9 aralkyl, C3-2o heteroalkyl or C3-12 cycloheteroalkyl group,

R ² and R ³ independently of one another represent hydrogen or an optionally substituted C 1-8 -alkyl, C 2-18 -alkenyl, C 2-22 -alkynyl, C 3-12 -cycloalkyl, C 3-12 -cycloalkenyl, C 7- 9-aralkyl, C3-28 heteroalkyl, C3-i2-cycloheteroalkyl, C5-i6 heteroaralkyl, phenyl, naphthyl or heteroaryl group or R2 and R3 together with the carbon atom connecting them to an optionally substituted 5-, 6-, 7-, 8- or 9-membered ring, which may optionally contain heteroatoms, and

R ^{4 is} hydrogen or a C-28-alkyl, C 2-18 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 increase the cleaning performance of peroxygen-containing detergents.

Use according to claim 1, characterized in that the concentration of the compound of formula (I) in aqueous liquor is 0.5 μιηοΙ / Ι to 500 μιηοΙ / Ι, in particular 5 μιηοΙ / Ι to 100 μιηοΙ / Ι.

Use according to claim 1 or 2, characterized in that the peroxygen concentration (calculated as H2O2) in the liquor in the range of 0.001 g / l to 10 g / l, in particular from 0.1 g / l to 1 g / l.

Detergent containing a peroxygen bleaching agent and a combination of a water-soluble builder system and a compound of formula (I)

in the R represents a CF3 or a Ο-28-alkyl, C2-alkenyl, C2-22-alkynyl, -i2-cycloalkyl, -i2-cycloalkenyl, phenyl, naphthyl, -9-aralkyl , -2o-heteroalkyl or -12-cycloheteroalkyl group,

R ² and R ³ independently of one another represent hydrogen or an optionally substituted C 1-8 -alkyl, C 2-6 alkenyl, C 2-12 -alkynyl, -i 2 -cycloalkyl, -i 2 -cycloalkenyl, -9-aralkyl-, Heteroalkyl, -i2-cycloheteroalkyl, -i6-heteroaralkyl, phenyl, naphthyl or heteroaryl group or R2 and R3 together with the carbon atom connecting them for an optionally substituted 5-, 6-, 7-, 8- or 9-membered ring, which may optionally contain heteroatoms, 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, -16-heteroaralkyl or an optionally substituted phenyl or naphthyl or heteroaryl group; stand.

5. Composition according to claim 4, characterized in that it contains 0.001 wt .-% to 5 wt .-%, in particular 0.05 wt .-% to 0.15 wt .-% of the compound according to formula (I).

6. Composition according to claim 4 or 5, characterized in that it contains the water-soluble builder system in an amount of up to 40 wt .-%, preferably 20 to 35 wt .-%, based on the agent.

7. Composition according to one of claims 4 to 6, characterized in that it contains peroxygen compounds in amounts of up to 50 wt .-%, in particular from 2 wt .-% to 45% by weight.

8. Composition according to one of claims 4 to 7, characterized in that a) it contains bleach activators in amounts of up to 10 wt .-%, in particular from 1, 5 wt .-% to 5 wt .-%, and / or b) the content of aluminosilicates, in particular zeolite, less than 5 wt .-%, preferably less than 3 wt .-%, more preferably less than 1 wt .-%, most preferably less than 0.5 wt .-% is, and / or c) the amount of alkali citrate is at most 5% by weight, preferably at most 0.5% by weight, more preferably 0% by weight, and / or d) the content of aminoalkane phosphonates, in particular DTPMP, is less than 2% by weight , preferably less than 1 wt .-%, more preferably less than 0, 1 wt .-%, most preferably 0 wt .-% based on the average.

9. Use according to one of claims 1 to 3 or agent according to one of claims 4 to 8, characterized in that the compound of the general formula (I) corresponds to the general formula (II),

in the R for a Ο-4-Alk lgruppe containing a substituent selected from

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 independently of one another R, hydrogen, halogen, a hydroxy, amino, an optionally substituted N-mono or

or C 2-4 -hydroxyalkylamino, N-phenyl or N-naphthylamino, C 2-8 -alkyl, C 1-12 -alkoxy, phenoxy, C 2-18 alkenyl, C 2-22 Alkynyl, C 3-12 cycloalkyl, C 3-12 cycloalkenyl, C 7-9 aralkyl, C 3-30 heteroalkyl, C 3-12 cycloheteroalkyl, C 5-6 heteroaralkyl, phenyl or naphthyl where the substituents are selected from Ο-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 Ci-6-alkyl-substituted rings are interconnected.

10. Use or composition according to any one of claims 1-9, characterized in that the soluble builder system of a) an alkali metal silicate with a module M20: SiO 2, wherein M is an alkali metal ion, in the range of 1: 1, 9 to 1 : 3.3, b) an alkali carbonate, c) a polymeric polycarboxylate having a molecular weight of less than 10000 g / mol, and d) a phosphonate capable of complexing, and e) optionally an acidic component.