EP3221441B1 - Détergent en dose unitaire à emballage hydrosoluble - Google Patents

Détergent en dose unitaire à emballage hydrosoluble Download PDF

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Publication number
EP3221441B1
EP3221441B1 EP15790539.9A EP15790539A EP3221441B1 EP 3221441 B1 EP3221441 B1 EP 3221441B1 EP 15790539 A EP15790539 A EP 15790539A EP 3221441 B1 EP3221441 B1 EP 3221441B1
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EP
European Patent Office
Prior art keywords
water
alkyl
partial composition
acid
acylhydrazone
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Not-in-force
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EP15790539.9A
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German (de)
English (en)
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EP3221441A1 (fr
Inventor
Michael Dreja
André HÄTZELT
Mirko Weide
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP3221441A1 publication Critical patent/EP3221441A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/3927—Quarternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames

Definitions

  • 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.
  • 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.
  • 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.
  • the content of peroxygen in the course of storage is significantly reduced, as is the content of bleach activators such as TAED.
  • bleach activators such as TAED.
  • enzymes 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.
  • bleaching agents such as, for example, sodium percarbonate and bleach activators which form peroxocarboxylic acid under perhydrolysis conditions, such as, for example, tetraacetylethylenediamine
  • bleach activators which form peroxocarboxylic acid under perhydrolysis conditions
  • 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.
  • 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).
  • 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 heteroa
  • 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.
  • 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.
  • 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.
  • 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-naphth
  • 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.
  • carboxylate such as lactate, citrate, tartrate or succinate, perchlorate, tetrafluoroborate, hexafluorophosphate, alkyl sulfonate, alkyl sulfate, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphat
  • 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 ⁇ m to 5000 ⁇ m, in particular from 50 ⁇ m to 1000 ⁇ m, 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 .
  • 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.
  • 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
  • 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.
  • peroxidic bleach particles have a particle size in the range from 10 ⁇ m to 5000 ⁇ m, in particular from 50 ⁇ m to 1000 ⁇ m 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.
  • 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 ⁇ m) 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.
  • 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.
  • 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 .
  • polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible.
  • 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.
  • 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.
  • 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.
  • 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.
  • the wrapping material dissolves, so that the detergent ingredients are released and can unfold their effect in the wash liquor.
  • 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.
  • the detergent may contain other ingredients which have the performance and / or aesthetics of the By means of further improvement.
  • 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.
  • 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.
  • 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) benz
  • bleach activating compounds such as nitriles, from which perimides acids may form under perhydrolysis conditions
  • nitriles 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,
  • 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 ⁇ m to 5000 ⁇ m, in particular from 50 ⁇ m to 1000 ⁇ m, 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 .
  • 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.
  • transition metal complexes 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)) - (2-pyridyl
  • 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 ⁇ 1-O-bridge two transition metal atoms.
  • the transition metal complexes may carry further, generally simpler ligands, in particular mono- or polyvalent anion ligands.
  • anion ligands 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.
  • 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.
  • 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.
  • 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-sulf
  • 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);
  • the acylhydrazone can also be used in the form of complex compounds of said metal central atoms with ligands of general formula (I)
  • 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.
  • organic anions such as citrate, oxalate, tartrate, formate, a C 2
  • metal ions 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.
  • 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.
  • EO ethylene oxide
  • 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).
  • 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.
  • 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 -Alkansulfonklaresalze, salts of SchwefelTexTexremonoestern with a fatty alcohol, a fatty acid soaps, salts of Schwefelklamonoestern with an ethoxylated fatty alcohol or a mixture of two or more of these anionic surfactants can.
  • 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 .-%.
  • 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.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -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.
  • the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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,
  • 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 .-%.
  • vinyl ethers such as vinylmethyl ethers, vinyl esters, ethylene, Propylene and styrene
  • the proportion of acid is at least 50 wt .-%.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • water-soluble inorganic builder materials may be included.
  • 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.
  • both ⁇ - and ⁇ -sodium disilicates are preferred.
  • 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.
  • 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.
  • 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.
  • 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.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • starch derivatives can be used, for example aldehyde starches.
  • 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.
  • 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.
  • 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.
  • enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which produces hydrogen peroxide in water.
  • 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.
  • 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 ,
  • 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.
  • 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.
  • 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.
  • mixtures of various foam inhibitors for example those of silicones, paraffins or waxes.
  • the foam inhibitors in particular silicone and / or paraffin-containing foam inhibitors, to a granular, water-soluble or dispersible carrier substance bound.
  • mixtures of paraffins and bistearylethylenediamide are preferred.
  • 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.
  • 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 3 Zeolite A - - 3 - CMC, Na salt - 3 3 - Silicone antifoam 1 1 1 1
  • Enzymes (amylase, protease, cellulase) - - - - dye +
  • Example 2 stain removal and hygiene performance
  • 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%.

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Claims (8)

  1. Détergent conditionné en portions dans un emballage en matériau hydrosoluble comportant deux compartiments, le détergent présentant une combinaison d'agent de blanchiment peroxyde et d'acylhydrazone de formule générale (I),
    Figure imgb0012
     dans laquelle R1 représente CF3 ou un groupe alkyle C1-C28, alcényle C2-C28, alcynyle C2-C22, cycloalkyle C3-C12, cycloalcényle C3-C12, cycloalkyle C3-C12, phényle, naphtyle, aralkyle C7-C9, hétéroalkyle C3-C20 ou cyclohétéroalkyle C3-C12, R1 et R3 représentent indépendamment un atome d'hydrogène ou un groupe alkyle C1-C28, alcényle C2-C28, alcynyle C2-C22, cycloalkyle C3-C12, cycloalcényle C3-C12, aralkyle C7-C9, hétéroalkyle C3-C28, cyclohétéroalkyle C3-C12, hétéroaralkyle C5-C16, phényle, naphtyle ou hétéroaryle éventuellement substitué, ou R2 et R3 forment conjointement avec l'atome de carbone qui les relie un cycle de 5, 6, 7, 8 ou 9 chaînons éventuellement substitué, lequel cycle peut éventuellement contenir des hétéroatomes, et R4 représente un atome d'hydrogène ou un groupe alkyle C1-C28, alcényle C2-C28, alcynyle C2-C22, cycloalkyle C3-C12, cycloalcényle C3-C12, aralkyle C7-C9, hétéroalkyle C3-C20, cyclohétéroalkyle C3-C12, hétéroaralkyle C5-C16 ou un groupe phényle, naphtyle ou hétéroaryle éventuellement substitué, le premier compartiment contenant une composition partielle liquide et la seconde chambre contenant une composition partielle solide, les compositions partielles différant d'au moins un constituant et/ou dans le contenu d'au moins un constituant, et une composition partielle présentant une acylhydrazone et une autre composition partielle présente séparément de celle-ci présentant un agent de blanchiment peroxyde, la première composition partielle ne présentant pas d'agent de blanchiment peroxyde et la seconde composition partielle ne présentant pas d'acylhydrazone, et la composition partielle dans laquelle l'acylhydrazone est présente ayant un pH allant jusqu'à pH 7 et la composition partielle dans laquelle l'agent de blanchiment peroxyde est présent ayant un pH supérieur à pH 7.
  2. Détergent conditionné en portions dans un emballage en matériau hydrosoluble comportant deux compartiments, présentant une combinaison d'agent de blanchiment peroxyde et d'acylhydrazone de formule générale (II),
    Figure imgb0013
     dans laquelle R1 représente un groupe alkyle C1-C4 ayant un substituant choisi
    Figure imgb0014
     dans lequel R10 représente un atome d'hydrogène ou un groupe alkyle C1-C28, alcényle C2-C28, alcynyle C2-C22, cycloalkyle C3-C12, cycloalcényle C3-C12, aralkyle C7-C9, hétéroalkyle C3-C20, cyclohétéroalkyle C3-C12, hétéroaralkyle C5-C16 et A- représente l'anion d'un acide organique ou inorganique, R2 et R4 sont tels que définis dans la formule (I), et R5, R6, R7 et R8 représentent indépendamment R1, un atome d'hydrogène, un atome d'halogène, un groupe hydroxy, amino, un groupe N-mono- ou di-C1-C4-alkyle ou hydroxyalkyle C2-C4-amino, N-phényl ou N-naphtyl-amino, alkyle C1-C28, alcoxy C1-C28, phénoxy, alcényle C2-C28, alcynyle C2-C22, cycloalkyle C3-C12, cycloalcényle C3-C12, aralkyle C7-C9, hétéroalkyle C3-C20, cyclohétéroalkyle C3-C12, hétéroaralkyle C5-C16, phényle ou naphtyle, les substituants étant choisis parmi les groupes alkyle C1-C4, alcoxy C1-C4, hydroxy, sulfo, sulfato, halogène, cyano, nitro, carboxy, phényle, phénoxy, naphtoxy, amino, N-mono ou dialkyle C1-C4 ou hydroxyalkylamino C2-C4, N-phényle ou N-naphtyl-amino, ou R5 et R6 ou R6 et R7 ou R7 et R8 étant reliés l'un à l'autre pour former 1, 2 ou 3 cycles carbocycliques ou O, NR10 ou S-hétérocycliques, éventuellement aromatiques et/ou éventuellement substitués par alkyle C1-C6, le premier compartiment contenant une composition partielle liquide et le second compartiment contenant une composition partielle solide, les compositions partielles différant d'au moins un constituant et/ou dans le contenu d'au moins un constituant, et une composition partielle présentant de l'acylhydrazone et une autre composition partielle présente séparément de celle-ci présentant un agent de blanchiment peroxyde, la première composition partielle ne présentant pas d'agent de blanchiment peroxyde et la seconde composition partielle ne présentant pas d'acylhydrazone, et la composition partielle dans laquelle l'acylhydrazone est présente ayant un pH allant jusqu'à pH 7 et la composition partielle dans laquelle l'agent de blanchiment peroxyde est présent ayant un pH supérieur à pH 7.
  3. Agent selon la revendication 1 ou 2, caractérisé en ce que l'emballage hydrosoluble du détergent est constitué d'un matériau en film hydrosoluble choisi parmi les polymères ou les mélanges de polymères hydrosolubles.
  4. Agent selon la revendication 3, caractérisé en ce que l'emballage hydrosoluble contient de l'alcool polyvinylique ou un copolymère d'alcool polyvinylique, et est constitué en particulier d'alcool polyvinylique ou de copolymère d'alcool polyvinylique.
  5. Agent selon l'une des revendications 1 à 4, caractérisé en ce que la composition partielle dans laquelle l'acylhydrazone est présent a un pH compris entre 2 et 4 et la composition partielle dans laquelle l'agent de blanchiment peroxyde est présent a un pH compris entre 9 et 12.
  6. Agent selon l'une des revendications 1 à 5, caractérisé en ce qu'il comprend 0,01 à 5 % en poids, en particulier 0,05 à 0,5 % en poids d'acylhydrazone et/ou d'agent de blanchiment peroxyde en quantités pouvant atteindre 60 % en poids, en particulier 5 % à 50 % en poids, et/ou des acides peroxocarboxyliques ou des agents de blanchiment formant des acides périmidiques dans des conditions de perhydrolyse, en quantités supérieures à 0 à 25 % en poids, en particulier à 0,5 à 10 % en poids.
  7. Agent selon l'une des revendications 1 à 6, caractérisé en ce qu'une portion emballée de manière hydrosoluble pèse 10 à 35 g, en particulier 12 à 28 g, dans lequel 0,3 à 2,5 g, en particulier 0,7 à 1,2 g pouvant être attribués à la proportion de l'emballage hydrosoluble contenue dans la spécification de poids.
  8. Agent selon l'une des revendications 1 à 7, caractérisé en ce que l'agent de blanchiment peroxyde est constitué de peracides organiques ou de sels peracides d'acides organiques, tels que l'acide phtalimidopercaproïque, l'acide perbenzoïque, l'acide monoperoxyphthalique et le diacide diperdodécano, et des sels de ceux-ci, tels que le monoperoxyphthalate de magnésium, les peroxydes de diacyle, le peroxyde d'hydrogène et les sels inorganiques, tels que du perborate alcalin, le percarbonate alcalin et/ou le persilicate alcalin, libérant du peroxyde d'hydrogène dans les conditions d'utilisation, et des composés d'inclusion de peroxyde d'hydrogène, tels que des produits d'insertion avec H2O2-urée, et des mélanges de ceux-ci.
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