EP3221441B1 - Water-soluble packaged unit dose detergent composition - Google Patents

Description

The present invention relates to portioned laundry detergents which are present in a water-soluble casing and which contain a combination of peroxidic bleach and certain bleach-enhancing active ingredient.

Modern detergents are often offered in liquid form and / or used at low temperatures. As liquid laundry detergents generally do not contain bleaches and conventional bleach systems used in solid detergents often reach their full effectiveness only at elevated temperatures, they may lack the desired bleaching performance and hygiene performance. In the long run, this can lead to bacterial contamination of washing machines and textiles and biofilm build-up in washing machines. It is sometimes recommended to counter this by occasional washing with a heavy-duty detergent at high temperature. However, some so-called heavy-duty detergents contain increasingly fewer bleach components, so that the addition of detergent additives with a higher bleach content is required in order to achieve a good bleaching and hygiene effect. Washing at high temperatures is also not sustainable.

Bleaching agents and bleach activators, especially if they are present side by side at the same time, often have only a limited storage stability. Thus, in peroxide bleaches, the content of peroxygen in the course of storage is significantly reduced, as is the content of bleach activators such as TAED. If enzymes are present, their activity usually also decreases during storage. Therefore, it is appropriate to protect various active components particularly when they are in particulate form, for example by coating, or spatially separating from each other. Coating or encapsulating the ingredients is a possible, but expensive and therefore expensive solution.

Conventional bleaching systems based on bleaching agents such as, for example, sodium percarbonate and bleach activators which form peroxocarboxylic acid under perhydrolysis conditions, such as, for example, tetraacetylethylenediamine, show an acceptable effect above about 40 ° C., which increases with increasing temperature. The aim is, however, to provide the consumer with a bleaching performance at low temperatures of about 20 ° C or 30 ° C without or with only acceptable damage to the laundry. For this, it is necessary to use a bleach-enhancing agent which has good action at low temperatures but does not cause high damage or wet-tissue rupture loss (such as some Mn-containing catalysts).

From the international patent application WO 2009/124855 For example, metal complexes with acylhydrazone ligands bearing electron-withdrawing substituents near the acyl group are known. From the international patent application WO 2012/080088 For example, acylhydrazones having cyclic ammonium groups are known as substituents in the vicinity of the acyl group. The US patent application US 2011/0240510 A1 relates to portion-wise packaged detergents containing a liquid component which may optionally be suspended in the liquid or may have a separate solid component in an additional compartment, wherein isoquinolinium salts may be part of the liquid or solid component. From the patent application DE 10 2012 219 359 A1 is the improvement of the antimicrobial effectiveness of detergents and cleaners by a combination of oxygenated bleach and acylhydrazone known.

in der R¹ für eine CF₃ oder für eine C_1-23-Alkyl-, C_2-28-Alkenyl-, C_2-22-Alkinyl-, C_3-12-Cycloalkyl-, C_3-12-Cycloalkenyl-, Phenyl-, Naphthyl-, C_7-9-Aralkyl, C_3-20-Heteroalkyl- oder C_3-12-Cycloheteroalkyl-gruppe,
R² und R³ unabhängig voneinander für Wasserstoff oder eine gegebenenfalls substituierte C_1-28-Alkyl-, C_2-28-Alkenyl-, C_2-22-Alkinyl-, C_3-12-Cycloalkyl-, C_3-12-Cycloalkenyl-, C_7-9-Aralkyl-, C_3-28-Heteroalkyl-, C_3-12-Cycloheteroalkyl-, C_5-16-Heteroaralkyl-, Phenyl-, Naphthyl- oder Heteroarylgruppe oder R2 und R3 zusammen mit dem sie verbindenden Kohlenstoffatom für einen gegebenenfalls substituierten 5-, 6-, 7-, 8- oder 9-gliedrigen Ring, der gegebenenfalls Heteroatome enthalten kann, und
R⁴ für Wasserstoff oder eine C_1-28-Alkyl-, C_2-28-Alkenyl-, C_2-22-Alkinyl-, C_3-12-Cycloalkyl-, C_3-12-Cycloalkenyl-, C_7-9-Aralkyl-, C_3-20-Heteroalkyl-, C_3-12-Cycloheteroalkyl-, C_5-16-Heteroaralkylgruppe oder eine gegebenenfalls substituierte Phenyl- oder Naphthyl- oder Heteroarylgruppe stehen, enthält, wobei die erste Kammer eine flüssige und die zweite Kammer eine feste Teilzusammensetzung enthält und sich die Teilzusammensetzungen mindestens in einem Inhaltsstoff und/oder in dem Gehalt mindestens eines Inhaltsstoffes unterscheiden, und wobei eine Teilzusammensetzung Acylhydrazon aufweist und eine getrennt davon vorliegende weitere Teilzusammensetzung peroxidisches Bleichmittel aufweist, wobei dann die erstgenannte Teilzusammensetzung kein peroxidisches Bleichmittel und die zweitgenannte Teilzusammensetzung kein Acylhydrazon aufweist, und dass die Teilzusammensetzung, in der sich das Acylhydrazon befindet, einen pH-Wert bis zu pH 7 und die Teilzusammensetzung, in der sich das peroxidische Bleichmittel befindet, einen pH-Wert von über pH 7 aufweist.The present invention is a laundry detergent packaged in portions in a wrapper of water-soluble material which comprises a combination of peroxidic bleach and acylhydrazone of the general formula (I),

in the R ^{1 is} a CF ₃ or a C _1-23 -alkyl, C _2-28 -alkenyl, C _2-22 -alkynyl, C _3-12 -cycloalkyl, C _3-12 -cycloalkenyl , Phenyl, naphthyl, C _7-9 -aralkyl, C _3-20 -heteroalkyl or C _3-12 -cycloheteroalkyl group,
R ² and R ³ are each independently hydrogen or an optionally substituted C _1-28 alkyl, C _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 Cycloalkenyl, C _7-9 aralkyl, C _3-28 heteroalkyl, C _3-12 cycloheteroalkyl, C _5-16 heteroaralkyl, phenyl, naphthyl or heteroaryl, or R 2 and R 3 together with them connecting carbon atom 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 _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 cycloalkenyl, C _7-9 Aralkyl, C _3-20 heteroalkyl, C _3-12 cycloheteroalkyl, C _5-16 heteroaralkyl or an optionally substituted phenyl or naphthyl or heteroaryl group, wherein the first chamber is a liquid and the second A sub-composition comprises at least one ingredient and / or at least one ingredient content, and wherein a sub-composition comprises acylhydrazone and a separate sub-composition comprising peroxide bleaching agent, in which case the former sub-composition does not contain a peroxidic bleach and the second part composition has no acylhydrazone and that the part composition in which the acylhydrazone is has a pH up to pH 7 and the partial composition in which the peroxidic bleach is present has a pH above pH 7.

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

In the compounds of general formula (I), R ^{2 is} preferably hydrogen. R ¹ and / or R ³ is preferably an electron-withdrawing group-substituted methyl, phenyl or naphthyl group. R ⁴ is preferably hydrogen. As the 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 optionally hetero-heteroatom-carrying heteroatom group.

Another object of the invention is described in claim 2.

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

trägt, in dem R¹⁰ für Wasserstoff oder eine C_1-23-Alkyl-, C_2-28-Alkenyl-, C_2-22-Alkinyl-, C_3-12-Cycloalkyl-, C_3-12-Cycloalkenyl-, C_7-9-Aralkyl-, C_3-20-Heteroalkyl-, C_3-12-Cycloheteroalkyl-, C_5-16-Heteroaralkylgruppe und A^- für das Anion einer organischen oder anorganischen Säure steht,
R² und R⁴ die für Formel (I) angegebenen Bedeutung haben und
R⁵, R⁶, R⁷ und R⁸ unabhängig voneinander für R¹, Wasserstoff, Halogen, eine Hydroxy-, eine Amino-, eine gegebenenfalls substituierte N-mono-oder di-C_1-4-alkyl- oder C_2-4-hydroxyalkyl-amino-, N-Phenyl- oder N-Naphthyl-amino-, C_1-23-Alkyl-, C_1-28-Alkoxy-, Phenoxy-, C_2-28-Alkenyl-, C_2-22-Alkinyl-, C_3-12-Cycloalkyl-, C_3-12-Cycloalkenyl-, C_7-9-Aralkyl-, C_3-20-Heteroalkyl-, C_3-12-Cycloheteroalkyl-, C_5-16-Heteroaralkyl-, Phenyl- oder Naphthylgruppe stehen, wobei die Substituenten ausgewählt werden aus C_1-4-Alkyl-, C_1-4-Alkoxy-, Hydroxy-, Sulfo-, Sulfato-, Halogen-, Cyano-, Nitro-, Carboxy-, Phenyl-, Phenoxy-, Naphthoxy-, Amino-, N-mono-oder di-C_1-4-alkyl- oder C_2-4-hydroxyalkyl-amino-, N-Phenyl- oder N-Naphthyl-aminogruppen, oder
R⁵ und R⁶ oder R⁶ und R⁷ oder R⁷ und R⁸ unter Ausbildung von 1, 2 oder 3 carbocyclischen oder O-, NR¹⁰- oder S-heterocyclischen, gegebenenfalls aromatischen und/oder gegebenenfalls C_1-6-alkylsubstituierten Ringen miteinander verbunden sind.Acylhydrazones include those of the general formula (II),

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

in which R ^{10 is} hydrogen or a C _1-23 -alkyl, C _2-28 -alkenyl, C _2-22 -alkynyl, C _3-12 -cycloalkyl, C _3-12 -cycloalkenyl, C _7-9 aralkyl, C _3-20 heteroalkyl, C _3-12 cycloheteroalkyl, C _5-16 heteroaralkyl, and A ^{- represents} the anion of an organic or inorganic acid,
R ² and R ^{4 have} the meaning given for formula (I) and
R ⁵ , R ⁶ , R ⁷ and R ⁸ independently of one another represent R ¹ , hydrogen, halogen, a hydroxy, an amino, an optionally substituted N-mono- or di-C _1-4 -alkyl or C _{2- 4} -hydroxyalkylamino, N-phenyl or N-naphthylamino, C _1-23 alkyl, C _1-28 alkoxy, phenoxy, C _2-28 alkenyl, C _2-22 Alkynyl, C _3-12 cycloalkyl, C _3-12 cycloalkenyl, C _7-9 aralkyl, C _3-20 heteroalkyl, C _3-12 cycloheteroalkyl, C _5-16 heteroaralkyl , Phenyl or naphthyl group, wherein the substituents are selected from C _1-4 alkyl, C _1-4 alkoxy, hydroxy, sulfo, sulfato, halogen, cyano, nitro, carboxy , Phenyl, phenoxy, naphthoxy, amino, N-mono or di-C _1-4 alkyl or C _2-4 hydroxyalkylamino, N-phenyl or N-naphthylamino groups, or
R ⁵ and R ⁶ or R ⁶ and R ⁷ or R ⁷ and R ⁸ to form 1, 2 or 3 carbocyclic or O, NR ¹⁰ - or S-heterocyclic, optionally aromatic and / or optionally C _1-6 alkyl substituted Rings are interconnected.

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

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

The acylhydrazones are preferably used in particulate form, wherein they can be converted into a desired particle shape with the aid of methods which are in principle conventional with the aid of in principle customary formulation auxiliaries, such as carrier materials and coating compositions. Acylhydrazone particles preferably have a particle size in the range from 10 μm to 5000 μm, in particular from 50 μm to 1000 μm, and / or a density from 0.85 g / cm ³ to 4.9 g / cm ³ , in particular from 0.91 g / cm ³ to 2.7 g / cm ³ . In agents according to the invention are preferably from 0.01 wt .-% to 5 wt .-%, in particular 0.05 wt .-% to 0.5 wt .-% acylhydrazone.

Suitable peroxidic bleaches are, in particular, organic peracids or pers acid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid, monoperoxyphthalic acid and diperdodecanedioic acid and salts thereof such as magnesium monoperoxyphthalate, diacyl peroxides, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the conditions of use, such as alkali metal perborate, alkali metal percarbonate and / or alkali metal per silicate, and hydrogen peroxide inclusion compounds such as H ₂ O ₂ -urea adducts, as well as mixtures of these. Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle. Particular preference is given to using alkali metal percarbonate, alkali metal perborate monohydrate or hydrogen peroxide. A detergent which can be used in the context of the invention comprises peroxidic bleach in amounts of preferably up to 60% by weight, in particular from 5% by weight to 50% by weight and particularly preferably from 15% by weight to 30% by weight. % or alternatively from 2.5% to 20% by weight, with sodium percarbonate being the most preferred peroxide bleaching agent. Preferably, peroxidic bleach particles have a particle size in the range from 10 μm to 5000 μm, in particular from 50 μm to 1000 μm and / or a density from 0.85 g / cm ³ to 4.9 g / cm ³ , in particular from 0, 91 g / cm ³ to 2.7 g / cm ³ .

One portion is an independent dosing unit with at least one chamber, is contained in the metered Good. A chamber is defined by walls (for example, by a film) delimited space, which is also without the material to be dosed (possibly with change its form) can exist. Thus, a surface coating or a surface coating layer is not an enclosure according to the present invention.

The walls of the chamber are made of a water-soluble material. The water solubility of the material can be determined by means of a square film of the said material (film: 22 × 22 mm with a thickness of 76 μm) fixed in a square frame (edge length on the inside: 20 mm) according to the following measurement protocol. Said framed film is immersed in 800 ml of distilled water heated to 20 ° C. in a 1 liter beaker with a circular bottom surface (Schott, Mainz, 1000 ml beaker, low mold), so that the surface of the clamped film is at right angles to the Bottom surface of the beaker is arranged, the upper edge of the frame is 1 cm below the water surface and the lower edge of the frame is aligned parallel to the bottom surface of the beaker such that the lower edge of the frame along the radius of the bottom surface of the beaker and the center of the lower edge of the frame is located above the center of the radius of the beaker bottom. The material dissolves with stirring (stirring speed magnetic stirrer 300 rpm, stirring bar: 5 cm long) within 600 seconds in such a way that with the naked eye, no single solid particles are more visible.

The walls of the chambers and thus the water-soluble wraps of the detergents according to the invention are preferably formed by a water-soluble film material. Such water-soluble packages can be made by either vertical form-fill sealing or thermoforming techniques.

The thermoforming process generally includes forming a first layer of water-soluble sheet material to form protrusions for receiving a composition therein, filling the composition into the protrusions, covering the composition-filled protrusions with a second layer of water-soluble sheet material, and sealing the first and second layers at least around the bulges.

The water-soluble film material is preferably selected from polymers or polymer blends. The wrapper may be formed of one or two or more layers of water-soluble film material. The water-soluble film materials of the first layer and the further layers, if present, may be the same or different.

It is preferable that the water-soluble wrapper contains polyvinyl alcohol or a polyvinyl alcohol copolymer; most preferably it consists of polyvinyl alcohol or polyvinyl alcohol copolymer.

Water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range of 10,000 to 1,000,000 gmol ^-1 , preferably 20,000 to 500,000 gmol ^-1 , more preferably 30,000 to 100,000 gmol ^-1 and especially from 40,000 to 80,000 gmol ^-1 .

The production of polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

Polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid, and / or mixtures of the above polymers may additionally be added to a film material suitable for producing the water-soluble coating. Also, the copolymerization of such polymers underlying monomers, individually or in mixtures of two or more, with vinyl acetate is possible.

Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic esters, methacrylic acid esters or mixtures thereof; among the esters, C _1-4 alkyl esters or hydroxyalkyl esters are preferred. Likewise preferred polyvinyl alcohol copolymers include ethylenically unsaturated dicarboxylic acids in addition to vinyl alcohol as further monomers. Suitable dicarboxylic acids are, for example, itaconic acid, maleic acid, fumaric acid and mixtures thereof, with itaconic acid being particularly preferred.

Suitable water-soluble films for use in the casings of the water-soluble packaging according to the invention are films sold by the company MonoSol LLC, for example under the designation M8630, C8400 or M8900. Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.

The detergent portion comprising the detergent and the water-soluble wrapper has two chambers.

The water-soluble enclosure has two chambers. The first chamber contains a liquid and the second chamber a solid part composition.

Preferably, the partial composition in which the acylhydrazone is located has a pH of from pH 2 to pH 4, and the partial composition in which the peroxidic bleaching agent is present has a pH of from pH 9 to pH 12; If the sub-compositions are not water-containing liquids, the pH in aqueous solutions is determined to be 0.5 g / l of the particular subcomposition, otherwise in the aqueous liquid as such.

The detergent is packaged in portions in a water-soluble wrapper, so that the user can give one or, if desired, several, preferably one, portions into the washing machine, in particular their dispensing compartment, or into a container for carrying out a hand washing process for a washing application. Such sachets meet the consumer's desire for simplified dosage. After addition of water, the wrapping material dissolves, so that the detergent ingredients are released and can unfold their effect in the wash liquor. Preferably, a water-soluble coated portion weighs 10 g to 35 g, in particular 12 g to 28 g and more preferably 12 g to 15 g, wherein 0.3 g to 2.5 g, in particular 0 to the content of the water-soluble coating contained in the weight , 7 g to 1.2 g omitted.

In addition to acylhydrazone and peroxidic bleach, the detergent may contain other ingredients which have the performance and / or aesthetics of the By means of further improvement. In the context of the present invention, the detergent preferably additionally contains one or more substances from the group of nonionic surfactants, anionic surfactants, builders, bleach activators, enzymes, electrolytes, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, antiredeposition agents, Graying inhibitors, anti-shrinkage agents, anti-wrinkling agents, color transfer inhibitors, antimicrobial agents, non-aqueous solvents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, skin-care agents, swelling and anti-slip agents, softening components and UV absorbers.

In addition to the acylhydrazone, bleach-activating peroxycarboxylic acid-yielding compound under perhydrolysis conditions, in particular compounds which give perbenzoic acid which is optionally substituted perhydrolysis and / or aliphatic peroxycarboxylic acids having 1 to 12 carbon atoms, in particular 2 to 4 carbon atoms, alone or in mixtures, be used. Suitable 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, especially nonanoyl or Isononanoyl- or Lauroyloxybenzolsulfonat (NOBS or iso-NOBS or LOBS) or Decanoyloxybenzoat (DOBA), their formal carbonic 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 (SOR-MAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetyl-fructose, tetraacetylxylose and octaacetyl lactose, acetylated it, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl-caprolactam.

in der R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_1-24-Alkyl- oder C_{2- 24}-Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN und-N⁽⁺⁾-CH₂-CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit mindestens einer, vorzugsweise zwei, gegebenenfalls substituierten C_1-24-Alkylgruppe(n) und gegebenenfalls weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, -CH₂-CH₃, CH₂-CH2-CH₃, -CH(CH₃)-CH₃,-CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6, R⁴ und R⁵ unabhängig voneinander eine voranstehend für R¹, R² oder R³ angegebene Bedeutung haben, wobei mindestens 2 der genannten Reste, insbesondere R² und R³, auch unter Einschluss des Stickstoffatoms und gegebenenfalls weiterer Heteroatome ringschließend miteinander verknüpft sein können und dann vorzugsweise einen Morpholino-Ring ausbilden, und X ein ladungsausgleichendes Anion, vorzugsweise ausgewählt aus Benzolsulfonat, Toluolsulfonat, Cumolsulfonat, den C_9-15-Alkylbenzolsulfonaten, den C_1-20-Alkylsulfaten, den C_8-22-Carbonsäure-methylestersulfonaten, Sulfat, Hydrogensulfat und deren Gemischen, ist, können eingesetzt werden. Unter Perhydrolysebedingungen Peroxocarbonsäuren oder Perimidsäuren bildende Bleichaktivatoren sind vorzugsweise in Mengen von über 0 Gew.-% (beispielsweise 0,01 Gew.-%) bis zu 25 Gew.-%, insbesondere 0,5 Gew.-% bis 10 Gew.-% in im Rahmen der Erfindung einsetzbaren Waschmitteln vorhanden. Vorzugsweise weisen Bleichaktivator-Partikel eine Teilchengröße im Bereich von 10 µm bis 5000 µm, insbesondere von 50 µm bis 1000 µm und/oder eine Dichte von 0,85 g/cm³ bis 4,9 g/cm³, insbesondere von 0,91 g/cm³ bis 2,7 g/cm³ auf. Falls das Waschmittel aus mehreren in einer wasserlöslichen Umhüllung mit zwei oder mehr Kammern enthaltenen Teilzusammensetzungen besteht, kann der unter Perhydrolysebedingungen Peroxocarbonsäure oder Perimidsäure bildende Bleichaktivator in der das Acylhydrazon enthaltenden Teilzusammensetzung oder vorzugsweise in der in diesem Fall aus teilchenförmigen Bestandteilen bestehenden, das peroxidische Bleichmittel enthaltenden Teilzusammensetzung enthalten sein.In addition to, or in place of, compounds which form peroxycarboxylic acids under perhydrolysis conditions, other bleach activating compounds, such as nitriles, from which perimides acids may form under perhydrolysis conditions, may be present. These include in particular aminoacetonitrile derivatives with quaternized nitrogen atom according to the formula

in which R ¹ is -H, -CH _3, a C _2-24 -alkyl or -alkenyl radical, a substituted C _1-24 alkyl or C _{2- 24} alkenyl group having at least one substituent from the group -Cl, -Br, -OH, -NH ₂ , -CN and-N ⁽⁺⁾ -CH ₂ -CN, an alkyl or alkenylaryl radical having a C _1-24 -alkyl group, or a substituted alkyl- or alkenylaryl radical having at least one, preferably two, optionally substituted C _1-24 alkyl group (s) and optionally further substituents on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (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 have the meaning given above for R ¹ , R ² or R ³ , where at least 2 of the radicals mentioned, in particular R ² and R ³ , also include the Sti and optionally a further morpholino ring, and X is a charge-balancing anion, preferably selected from benzenesulfonate, toluenesulfonate, cumene sulfonate, the C _9-15 -alkylbenzenesulfonates, the C _1-20 -alkyl sulfates, C _{8-22 carboxylic} acid methyl ester sulfonates, sulfate, hydrogen sulfate and mixtures thereof can be used. Under perhydrolysis conditions peroxycarboxylic acids or perimic acids forming bleach activators are preferably in amounts of over 0 wt .-% (for example, 0.01 wt .-%) up to 25 wt .-%, in particular 0.5 wt .-% to 10 wt .-% present in detergents which can be used in the context of the invention. Bleach activator particles preferably have a particle size in the range from 10 μm to 5000 μm, in particular from 50 μm to 1000 μm, and / or a density from 0.85 g / cm ³ to 4.9 g / cm ³ , in particular from 0.91 g / cm ³ to 2.7 g / cm ³ . If the detergent is a plurality of partial compositions contained in a water-soluble envelope having two or more chambers, the peracid peracid or perimidic acid forming perhydrolysis agent may comprise the partial composition containing the acylhydrazone or, preferably, the partial composition containing the peroxidic bleach be included.

The additional presence of bleach-catalyzing transition metal complexes is possible. 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, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,5,9-trimethyl -1,5,9-triazacyclododecane, (bis ((1-methylimidazol-2-yl) methyl)) - (2-pyridylmethyl) amine, N, N '- (bis (1-methylimidazole-2-yl) 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 (bis) 2-benzimidazolyl-methyl) 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 asymmetrically or μ1-O-bridge two transition metal atoms. 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 useful transition metal complex compounds are [N, N'-bis [(2-hydroxy-5-vinylphenyl) methylene] -1,2-diamino-cyclohexane] -manganese (III) chloride, [N, N ' -Bis [(2-hydroxy-5-nitrophenyl) methylene] -1,2-diamino-cyclohexane] 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, nitrite pentammine cobalt (III) chloride, hexaminocobalt (III) chloride, chloropentammine cobalt ( III) chloride and the peroxo complex [(NH ₃ ) ₅ Co-OO-Co (NH ₃ ) ₅ ] Cl ₄ . The performance of the acylhydrazones may optionally be enhanced by the presence of manganese, titanium, cobalt, nickel or copper ions, preferably Mn (II) - (III) - (IV) - (V), Cu (I) - (II) - (III), Fe (I) - (II) - (III) - (IV), Co (I) - (II) - (III), Ni (I) - (II) - (III), Ti ( II) - (III) - (IV) and more 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 comprising a ligand having a skeleton of formula (I) or formula (II), may have the corresponding ligand one or more times, 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 H ₂ O, NH ₃ , CH ₃ OH, acetylacetone, terpyridine, organic anions such as citrate, oxalate, tartrate, formate, a C _2-18 -carboxylate, a C _1-18 alkyl sulfate, especially methosulfate, or a corresponding alkanesulfonate, inorganic anions such as halide, especially chloride, perchlorate, tetrafluoroborate, hexafluorophosphate, nitrate, bisulfate, hydroxide or hydroperoxide. It may also have bridging ligands such as alkylenediamines. 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.

The detergent may contain nonionic surfactants. Suitable nonionic surfactants include alkoxylated fatty alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl polyglucosides, and mixtures thereof.

The alkoxylated fatty alcohols used are preferably ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 4 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear. In particular, alcohol ethoxylates having 12 to 18 C atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 5 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 4 EO or 7 EO, C _9-11 alcohols with 7 EO, C _12-18 alcohols with 5 EO or 7 EO and mixtures of these. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention. Also suitable are also a mixture of a (more) branched ethoxylated fatty alcohol and an unbranched ethoxylated fatty alcohol, such as a mixture of a C _16-18 fatty alcohol with 7 EO and 2-propylheptanol with 7 EO. The amount of nonionic surfactant is preferably up to 25 wt .-%, in particular 1 wt .-% to 20 wt .-%, wherein the statement of wt .-% here and below in each case based on the total detergent, if not stated otherwise.

The detergent may contain, in place of the nonionic surfactant or, preferably, additionally an anionic surfactant.

Suitable anionic surfactant include alkylbenzenesulfonic acid salts, olefinsulfonic, C _{12- 18} -Alkansulfonsäuresalze, salts of Schwefelsäuremonoestern with a fatty alcohol, a fatty acid soaps, salts of Schwefelsäuremonoestern with an ethoxylated fatty alcohol or a mixture of two or more of these anionic surfactants can. Of these anionic surfactants, alkylbenzenesulfonic acid salts, fatty acid soaps and mixtures thereof are particularly preferred.

The content of anionic surfactant is preferably up to 30 wt .-%, in particular 1 wt .-% to 25 wt .-%.

Examples of surfactants of the sulfonate type are C _3-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous Sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained. Also suitable are C _12-18 alkanesulfonates and 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.

Alk (en) ylsulfates are the salts of sulfuric monoesters of C ₁₂ -C ₁₃ fatty alcohols, for example coconut oil fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half esters secondary alcohols of these chain lengths are preferred. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred.

Also, fatty alcohol ether sulfates, such as the sulfuric acid monoesters of straight-chain or branched C _7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C _{12 -18} fatty alcohols with 1 to 4 EO are suitable.

Further suitable anionic surfactants are fatty acid soaps. Suitable are saturated and unsaturated 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, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.

The anionic surfactants including the fatty acid soaps may be in the form of their sodium, potassium or magnesium or ammonium salts. Preferably, the anionic surfactants are in Form their sodium salts or ammonium salts. Amines which can be used for the neutralization are preferably choline, triethylamine, monoethanolamine, diethanolamine, triethanolamine, methylethylamine or a mixture thereof, with monoethanolamine being preferred. In a particularly preferred embodiment, the detergent contains, in particular when in liquid form or liquid partial compositions, monoethanolamine-neutralized alkylbenzenesulfonic acid, in particular C _9-13 -alkylbenzenesulfonic acid, and / or monoethanolamine-neutralized fatty acid.

The detergents may contain water, wherein the content of water in preferred embodiments is less than 10 wt .-%, in particular less than 8 wt .-%. If the detergent consists of several partial compositions, preferably less than 10% by weight, in particular less than 8% by weight, of water is also contained in each partial composition. A detergent may, especially if it is in liquid, gel or pasty form, contain water-miscible solvent. These include, for example, monohydric alcohols having 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols and triols having 2 to 4 carbon atoms, in particular ethylene glycol, propylene glycol and glycerol, and mixtures thereof and those from the mentioned compound classes derivable ether. Such water-miscible solvents are preferably present in the compositions according to the invention in amounts of not more than 30% by weight, in particular from 6% by weight to 20% by weight.

A detergent 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 glycinediacetic acid, methylglycinediacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamine-N, N'-disuccinic acid and hydroxyiminodisuccinates, ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), 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 thereof which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality. The relative average molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g / mol and 200,000 g / mol, 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, though 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 acid is at least 50 wt .-%. 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 C ₃ -C ₈ -carboxylic acid and preferably from a C ₃ -C ₄ monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ -dicarboxylic acid, 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 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 can also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C ₁ -C ₄ -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives , is substituted. Preferred terpolymers contain 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 Methallylsulfonat 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 have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate. The organic builder substances can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

If desired, such organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Quantities in the upper half of said ranges are preferably used in pasty or liquid, in particular hydrous, agents.

Suitable water-soluble inorganic builder materials are, in particular, polyphosphates, preferably sodium triphosphate. As water-insoluble inorganic builder materials are in particular crystalline or amorphous, water-dispersible alkali metal aluminosilicates, in amounts not exceeding 25 wt .-%, preferably from 3 wt .-% to 20 wt .-% and in particular in amounts of 5 wt .-% to 15 wt. -% used. Among these, the detergent-grade crystalline sodium aluminosilicates, particularly zeolite A, zeolite P, and zeolite MAP, and optionally zeolite X, are preferred. Amounts near the above upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m. Their calcium binding capacity is generally in the range of 100 to 200 mg CaO per gram.

In addition to or as an alternative to said water-insoluble aluminosilicate and alkali carbonate, further 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 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 1: 2 to 1: 2.8. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula of Na ₂ Si _x O used _{2x + 1} · y H ₂ O in which x, known as the modulus, an integer of 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates (Na ₂ Si ₂ O ₅ .yH ₂ O) are preferred. Also prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali metal silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, can be used in 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 1.9 to 3.5 are used in a further embodiment. In a preferred embodiment of such agents, a granular compound of alkali silicate and alkali carbonate is used, as is commercially available, for example, under the name Nabion® 15.

Suitable enzymes which can be used in the compositions are those from the class of the proteases, amylases, lipases, cutinases, pullulanases, hemicellulases, cellulases, oxidases, laccases and peroxidases and mixtures thereof. Particularly suitable are from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia or Coprinus cinereus derived enzymatic agents. The enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are preferably present in the detergents or cleaners according to the invention in amounts of up to 5% by weight, in particular from 0.002% by weight to 4% by weight. If the agent of the invention contains protease, it preferably has a proteolytic activity in the range of about 100 PE / g to about 10,000 PE / g, in particular 300 PE / g to 8000 PE / g. If several enzymes are to be used in the agent according to the invention, this can be carried out by incorporation of the two or more separate or in a known manner separately prepared enzymes or by two or more enzymes formulated together in a granule.

In order to establish a desired pH, which does not result from the mixture of the other components, the compositions according to the invention can contain system- and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid. but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are present in the compositions according to the invention in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.

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

If desired, the compositions may contain a customary color transfer inhibitor, then preferably in amounts of up to 2% by weight, in particular from 0.1% by weight to 1% by weight, which in a preferred embodiment is selected from the polymers of vinylpyrrolidone , Vinylimidazole, Vinylpyridine N-oxide or the copolymers of these. Useful are both polyvinylpyrrolidones having molecular weights of from 15,000 g / mol to 50,000 g / mol and also polyvinylpyrrolidones having higher molecular weights of, for example, up to more than 1,000,000 g / mol, in particular from 1,500,000 g / mol to 4,000,000 g / mol, N-vinylimidazole / N-vinylpyrrolidone copolymers, polyvinyloxazolidones, copolymers based on vinyl monomers and carboxamides, pyrrolidone group-containing polyesters and polyamides, grafted polyamidoamines and polyethyleneimines, polyamine-N-oxide polymers and polyvinyl alcohols. However, it is also possible to use enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which produces hydrogen peroxide in water. The addition of a mediator compound for the peroxidase, for example an acetosyringone, a phenol derivative or a phenotiazine or phenoxazine, is preferred in this case, whereby also above-mentioned polymeric Farbübertragungsinhibitorwirkstoffe can be used. Polyvinylpyrrolidone preferably has an average molecular weight in the range from 10,000 g / mol to 60,000 g / mol, in particular in the range from 25,000 g / mol to 50,000 g / mol. Among the copolymers, preference is given to those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5: 1 to 1: 1 with an average molar mass in the range from 5,000 g / mol to 50,000 g / mol, in particular 10,000 g / mol to 20,000 g / mol , However, in preferred embodiments of the invention, the detergents are free of such additional color transfer inhibitors.

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

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

The preparation of solid agents presents no difficulties and may be accomplished in a known manner, for example by spray-drying or granulation, with enzymes and any other thermally-sensitive ingredients, such as bleach, optionally added separately later. For the production of 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.

Liquid or pasty compositions in the form of conventional solvent-containing solutions are usually prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.

Example 1: Composition

In Table 1, the compositions are listed in 2-chamber pouches of water-soluble polyvinyl alcohol film packaged inventive agent E1 to E4 (data in% by weight based on the respective chamber contents). Table 1: medium E1 E2 E3 E4 Chamber 1, 17 g C _9-13 alkyl benzene sulphonate, Na salt - 5 10 - C _12-14 fatty alcohol with 7 EO - 5 - - sodium 90 60 60 70 TAED - - - 15 C _12-18 fatty acid, Na salt - - 5 - PVA / maleic acid copolymer - - 2 - Phosphonic acid, Na salt - 0.5 0.5 0.5 sodium - 20 10 - Sodium silicate (2.0) - - 3 3 Zeolite A - - 3 - CMC, Na salt - 3 3 - Silicone antifoam 1 1 1 1 Enzymes (amylase, protease, cellulase) - - - - dye + + + + Soil-release polymer ^a) - - 2 - Perfume - - - Optical brightener 0.3 0.3 0.3 0.3 sodium bicarbonate - - - 5 sodium sulphate At 100 At 100 At 100 At 100 Chamber 2, 10 g C _9-13 alkyl benzene sulphonate, MEA salt - - - 30 C _13-15 fatty alcohol with 8 EO - - - 30 TAED 50 50 50 - C _12-18 fatty acid, MEA salt - - - 3 PVA / maleic acid copolymer - - - - Citric acid, Na salt - 10 10 3 Phosphonic acid, Na salt 0.5 0.5 0.5 0.5 glycerin - - - 12 Monoethanolamine - - - 3 Acylhydrazone ^b) 0.25 0.25 0.25 0.25 CMC, Na salt - - 2 - Silicone antifoam 1 1 1 1 Enzymes (amylase, protease, cellulase) + + + dye + + + + Target Release Polymer ^c) - - - 2 Perfume 0.5 0.5 0.5 0.5 Optical brightener - - 0.3 0.3 sodium sulphate At 100 At 100 At 100 - propylene glycol - - - At 100 a) Texcare® SRA. 300, Clariant
b) N - [(2-Hydroxyphenyl) methyleneamino] -2- (4-methylmorpholin-4-ium-4-yl) acetamide chloride
c) Texcare® SRN 170, Clariant

Example 2: stain removal and hygiene performance

27 g of a detergent containing 17 g of sodium percarbonate, 5 g of tetraacetylethylenediamine and ingredients given in Table 1, and 0.25 g of the acylhydrazone N - [(2-hydroxyphenyl) methyleneamino] -2- (4-methylmorpholin-4-ium-4 -yl) acetamide chloride were extracted into deep-drawn pouches 0.9 g of a water-soluble polyvinyl alcohol film (Monosol) introduced, wherein in a variant (A) the said 3 components sodium percarbonate, tetraacetylethylenediamine and acylhydrazone together in a 1-chamber pouch and in another variant (B) sodium percarbonate and tetraacetylethylenediamine into the first chamber and the acylhydrazone into the second chamber of a 2-chamber pouch. For comparison (C), an otherwise variant A corresponding experiment was carried out without acylhydrazone.

Standardized test soils from blueberry juice, blackberry juice, tea, red wine, and blackcurrant on cotton were each washed with 1 pouch of the detergent in a washing machine (Miele® W918, 60 minutes main wash, water 16 ° dH, 3.5 kg prewashed standard cotton textiles as a load, addition of standardized ballast soil) at 20 ° C or 30 ° C. Table 2 shows the relative change in remission relative to baseline as the mean across the 5 standardized test soils (larger values indicate greater stain removal performance). Stain removal performance values are given for freshly prepared agents. After storage (4 weeks, 40 ° C, 50% humidity), Agent B exhibited a 8.3% reduction in stain removal performance at 30 ° C and Agent A at 30 ° C reduced stain removal performance by 14.9%.

To determine the bactericidal efficacy, laboratory tests according to EN 1276 with relative dilution corresponding to a quantity of water of 17 l, simulated low load and the test organism Staphylococcus aureus ATCC 6538 were carried out with the pouches. Table 2 also shows the reduction of the live cell count of the test strain as a measure of the hygiene performance of the agents. Table 2: Stain removal and hygiene performance stain removal hygiene A, 30 ° C 74 > 1,2E05 A, 20 ° C 69 4,2E04 B, 30 ° C 72 > 1, 2E05 B, 20 ° C 68 > 1, 2E05 C, 30 ° C 72 > 1,2E05 C, 20 ° C 59 nb nb: not determined

Claims (8)

1. A washing agent packaged in portions in a wrapping which is made of a water-soluble material and has two chambers, which washing agent contains a combination of a peroxidic bleaching agent and acylhydrazone of the general formula (I),

   

   in which R¹ represents a CF₃ or a C_1-28 alkyl, C_2-28 alkenyl, C_2-22 alkinyl, C_3-12 cycloalkyl, C_3-12 cycloalkenyl, phenyl, naphthyl, C_7-9 aralkyl, C_3-20 heteroalkyl or C_3-12 cycloheteroalkyl group, R¹ and R³ represent, independently of one another, hydrogen or an optionally substituted C_1-28 alkyl, C_2-28 alkenyl, C_2-22 alkinyl, C_3-12 cycloalkyl, C_3-12 cycloalkenyl, C_7-9 aralkyl, C_3-28 heteroalkyl, C_3-12 cycloheteroalkyl, C_5-16 heteroaralkyl, phenyl, naphthyl or heteroaryl group, or R² and R³, together with the carbon atom which binds them, represent an optionally substituted 5-, 6-, 7-, 8- or 9- membered ring which can optionally contain heteroatoms, and R⁴ represents hydrogen or a C_1-28 alkyl, C_2-28 alkenyl, C_2-22 alkinyl, C_3-12 cycloalkyl, C_3-12 cycloalkenyl, C_7-9 aralkyl, C_3-20 heteroalkyl, C_3-12 cycloheteroalkyl, C_5-16 heteroaralkyl group or an optionally substituted phenyl or naphthyl or heteroaryl group, wherein the first chamber contains a liquid partial composition and the second chamber contains a solid partial composition, and the partial compositions differ from one another in at least one ingredient and/or in the content of at least one ingredient, and wherein a partial composition comprises acylhydrazone and a further partial composition which is separate therefrom comprises a peroxidic bleaching agent, wherein the former partial composition does not comprise a peroxidic bleaching agent and the latter partial composition does not comprise acylhydrazone, and the partial composition in which the acylhydrazone is present has a pH of up to pH 7, and the partial composition in which the peroxidic bleaching agent is present has a pH that is higher than pH 7.
2. The washing agent packaged in portions in a wrapping which is made of a water-soluble material and has two chambers, which washing agent contains a combination of a peroxidic bleaching agent and acylhydrazone of the general formula (II),

   

   in which R¹ represents a C_1-4 alkyl group which carries a substituent selected from

   

   in which R¹⁰ represents hydrogen or a C_1-28 alkyl, C_2-28 alkenyl, C_2-22 alkinyl, C_3-12 cycloalkyl, C_3-12 cycloalkenyl, C_7-9 aralkyl, C_3-20 heteroalkyl, C_3-12 cycloheteroalkyl, C_5-16 heteroaralkyl group and A^- represents the anion of an organic or inorganic acid, R² and R⁴ have the meaning specified for formula (I) and R⁵, R⁶, R⁷ and R⁸ represent, independently of one another, R¹, hydrogen, halogen, a hydroxy group, amino group, an optionally substituted N-mono-C_1-4 alkyl or di-C_1-4 alkyl or C_2-4 hydroxyalkyl amino, N-phenyl or N-naphthyl amino, C_1-28 alkyl, C_1-28 alkoxy, phenoxy, C_2-28 alkenyl, C_2-22 alkinyl, C_3-12 cycloalkyl, C_3-12 cycloalkenyl, C_7-9 aralkyl, C_3-20 heteroalkyl, C_3-12 cycloheteroalkyl, C_5-16 heteroaralkyl, phenyl or naphthyl group, wherein the substitutes are selected from C_1-4 alkyl, C_1-4 alkoxy, hydroxy, sulfo, sulfato, halogen, cyano, nitro, carboxy, phenyl, phenoxy, naphthoxy, amino, N-mono- or di-C_1-4 alkyl or C_2-4 hydroxyalkyl amino, N-phenyl or N-naphthyl amino groups, or R⁵ and R⁶ or R⁶ and R⁷ or R⁷ and R⁸ are interconnected, forming 1, 2 or 3 carbocyclic or O-, NR¹⁰ or S-heterocyclic, optionally aromatic and/or optionally C_1-6 alkyl-substituted rings, wherein the first chamber contains a liquid partial composition and the second chamber contains a solid partial composition, and the partial compositions differ from one another in at least one ingredient and/or in the content of at least one ingredient, and wherein a partial composition comprises acylhydrazone and a further partial composition which is separate therefrom comprises a peroxidic bleaching agent, wherein the former partial composition does not comprise a peroxidic bleaching agent and the latter partial composition does not comprise acylhydrazone, and the partial composition in which the acylhydrazone is present has a pH of up to pH 7 and the partial composition in which the peroxidic bleaching agent is present has a pH that is higher than pH 7.
3. The agent according to claim 1 or 2, characterized in that the water-soluble wrapping of the washing agent is formed by a water-soluble film material selected from water-soluble polymers or polymer mixtures.
4. The agent according to claim 3, characterized in that the water-soluble wrapping contains polyvinyl alcohol or a polyvinyl alcohol copolymer, in particular consists of polyvinyl alcohol or a polyvinyl alcohol copolymer.
5. The agent according to one of claims 1 to 4, characterized in that the partial composition in which the acylhydrazone is present has a pH of pH 2 to pH 4, and the partial composition in which the peroxidic bleaching agent is present has a pH of pH 9 to pH 12.
6. The agent according to one of claims 1 to 5, characterized in that it comprises 0.01 wt.% to 5 wt.%, in particular 0.05 wt.% to 0.5 wt.%, of acylhydrazone and/or a peroxidic bleaching agent in amounts of up to 60 wt.%, in particular 5 wt.% to 50 wt.%, and/or comprises bleach activators, which form peroxocarboxylic acids or perimidic acids under perhydrolysis conditions, in amounts of greater than 0 wt.% to 25 wt.%, in particular 0.5 wt.% to 10 wt.%.
7. The agent according to one of claims 1 to 6, characterized in that a water-soluble wrapped portion weighs 10 g to 35 g, in particular 12 g to 28 g, the proportion of water-soluble wrapping contained in the specified weight accounting for 0.3 g to 2.5 g, in particular 0.7 g to 1.2 g.
8. The agent according to one of claims 1 to 7, characterized in that the peroxidic bleaching agent is selected from organic peracids or peracid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid, monoperoxyphthalic acid, and diperdodecane diacid, and salts thereof, such as magnesium monoperoxyphthalate, diacyl peroxides, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the conditions of use, such as alkali perborate, alkali percarbonate and/or alkali persilicate, and hydrogen peroxide inclusion compounds, such as H₂O₂ urea adducts, and mixtures thereof.