EP3277786A1 - Composition de détergent à élimination améliorée des taches - Google Patents

Composition de détergent à élimination améliorée des taches

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Publication number
EP3277786A1
EP3277786A1 EP16712050.0A EP16712050A EP3277786A1 EP 3277786 A1 EP3277786 A1 EP 3277786A1 EP 16712050 A EP16712050 A EP 16712050A EP 3277786 A1 EP3277786 A1 EP 3277786A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
weight
acid
phenyl
alkenyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP16712050.0A
Other languages
German (de)
English (en)
Inventor
Nicole BODE
Brigitte Giesen
Annika GÜLDNER
André HÄTZELT
Hauke Rohwer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP3277786A1 publication Critical patent/EP3277786A1/fr
Ceased legal-status Critical Current

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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
    • 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
    • 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

Definitions

  • the present invention relates to the use of a combination of water-soluble builder systems and certain acylhydrazones to improve stain removal, especially bleachable, hydrophilic stains such as red wine stains, tea stains, red fruit stains or beverages and foods thereof, or those containing corresponding dyes, from laundry detergents Washing textiles or cleaning hard surfaces, as well as detergents containing such a combination.
  • acylhydrazones as bleach catalyst, as described in WO 2013/104631 A1, leads to improved removal of the abovementioned stains, even at low temperatures.
  • the optimal effect depends on the interaction with other components of the formulation.
  • the cleaning performance in formulations in which the bleach catalyst is used in combination with a water-soluble builder system is improved.
  • a first subject of the invention is therefore the use of a combination of a water-soluble builder system with an acylhydrazone of the general formula (I),
  • R is a CF3 or for a ⁇ -alkyl, C2-28 alkenyl, C2-22 alkynyl, C3-i2-cycloalkyl, C3 cycloalkenyl, phenyl, naphthyl, C7-9 aralkyl , C3-2o-heteroalkyl or C3-i2-cycloheteroalkyl,
  • R 2 and R 3 are independently hydrogen or an optionally substituted C1 alkyl, C2-28 alkenyl, C2-22 alkynyl, C3-i2-cycloalkyl -, C3-i2-Cycloalkenyl-, C7-9-aralkyl, C3 heteroalkyl, C3-i2-cycloheteroalkyl, -i6-heteroaralkyl, phenyl, naphthyl or heteroaryl group or R2 and R3 together with the carbon atom connecting them for an optionally substituted 5-, 6-, 7-, 8- or 9
  • R 4 is hydrogen or a C 1-6 -alkyl, C 2-30 alkenyl, C 2-22 -alkynyl, C 3-12 -cycloalkyl, C 3-6 cycloalkenyl, C 7-9 -aralkyl, C 3-30 -heteroalkyl-, C3-i2-cycloheteroalkyl, Cs-i6-heteroaralkyl group or an optionally substituted phenyl or naphthyl or heteroaryl group, to increase the cleaning power of peroxygen-containing detergents.
  • Another object of the invention are detergents containing a peroxygen bleaching agent and a combination of water-soluble builder system and a compound of formula (I).
  • Yet another aspect of the invention relates to a process for washing textiles in which an agent according to the invention is used.
  • At least one refers to 1 or more, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or more, and does not refer to components of the compositions described herein
  • one or more different anionic surfactants ie, at least one anionic surfactant
  • the quantities refer to the total amount of the corresponding designated type of ingredient as defined above.
  • Water-soluble refers to a solubility in water at 20 ° C of at least 1 g / L, preferably at least 10 g / L.
  • cleaning power is understood to mean the removal of one or more stains, in particular laundry stains, which are bleach-sensitive.
  • the distance can be measured by a brightening of the soiling measured as well as assessed visually.
  • the detergents described herein may be detergents for textiles or natural fibers.
  • Detergents in the context of the invention also include washing aids, which in the manual or machine textile laundry be dosed to the actual detergent to achieve a further effect or to enhance an effect.
  • laundry detergents within the scope of the invention also include textile pre-treatment and post-treatment agents, ie those agents with which the laundry item is brought into contact before the actual laundry, for example for dissolving stubborn soiling, and also agents which are in a downstream of the actual textile laundry step give the laundry further desirable properties such as comfortable grip, crease resistance or low static charge.
  • the fabric softeners are calculated.
  • acylhydrazones of formula (I) may be in E or Z configuration; when R 2 is hydrogen, the compound of general formula (I) may be in one of its tautomeric forms or as a mixture of these.
  • R 2 is preferably hydrogen.
  • R and / or R 3 is preferably an electron-withdrawing group-substituted methyl, phenyl or naphthyl group.
  • R 4 is preferably hydrogen.
  • an electron-withdrawing group is preferably an ammonium group in question, which optionally carries alkyl or hydroxyalkyl groups or is formed with the inclusion of the N-atom carrying an alkyl group as heterocycloalkyl optionally carrying further heteroatoms.
  • Preferred embodiments of the compounds according to general formula (I) include those of general formula (II),
  • R 10 is hydrogen or a ⁇ -28-alkyl, C 2-30 alkenyl, C 2-22 alkynyl, C 3-12 cycloalkyl, C 3-12 cycloalkenyl, C 7-9 aralkyl, C 3- 2o-heteroalkyl, C3-i2-cycloheteroalkyl, C5-i6-heteroaralkyl and A "represents the anion of an organic or inorganic acid,
  • R 2 and R 4 have the meaning given for formula (I) and R 5 , R 6 , R 7 and R 8 independently of one another R, hydrogen, halogen, a hydroxy, amino, an optionally substituted N-mono or di-Ci-4-alkyl or C2-4-hydroxyalkyl amino, N-phenyl or N-naphthyl-amino, C-28-alkyl, C-28-alkoxy, phenoxy, C 2-18 -alkenyl, C 2-22 -alkynyl, C 3-12 Cycloalkyl, C 3-12 cycloalkenyl, Cz-g aralkyl, C 3-30 heteroalkyl, C 3-12 cycloheteroalkyl, C 5-16 heteroaralkyl, phenyl or naphthyl, wherein the substituents are selected from Ci-4-alkyl, hydroxy, sulfo, sulfato, halogen, cyano, nitro, carboxy,
  • R 5 and R 6 or R 6 and R 7 or R 7 and R 8 to form 1, 2 or 3 carbocyclic or O, NR 10 - or S-heterocyclic, optionally aromatic and / or optionally C 1-6 alkyl-substituted rings connected to each other.
  • the anion A " is preferably a carboxylate such as lactate, citrate, tartrate or succinate, perchlorate, tetrafluoroborate, hexafluorophosphate, alkyl sulfonate, alkyl sulfate, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, isocyanate, rhodanide, nitrate, fluoride, chloride, bromide, bicarbonate or carbonate, wherein in polyvalent anions, the charge balance can be achieved by the presence of additional cations such as sodium or ammonium ions.
  • a carboxylate such as lactate, citrate, tartrate or succinate, perchlorate, tetrafluoroborate, hexafluorophosphate, alkyl sulfonate, alkyl sulfate, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate
  • the performance of compounds of general formula (I) may optionally be enhanced by the presence of manganese, titanium, cobalt, nickel or copper ions, preferably Mn (II) - (II) - (IV) - (V), Cu (I) - (II) - (III), Fe (I) - (II) - (III) - (IV), Co (I) - (II) - (III), Ni (I) - (II) - (III), Ti (II) - (III) - (IV) and particularly preferably those selected from Mn (II) - (III) - (IV) - (V), Cu (I) - (II) - ( III), Fe (I) - (II) - (III) - (IV) and Co (I) - (II) - (III);
  • 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 which has a ligand with a skeleton of the formula (I) may have the corresponding ligand once or more than once, in particular twice. It may be one or possibly two or more nuclear. It may also contain other neutral, anion or cationic ligands such as H2O, NH3, CH3OH, acetylacetone, terpyridine, organic anions such as citrate, oxalate, tartrate, formate, a C2-is-carboxylate, a Ci-ie-alkyl - sulfate, in particular methosulfate, or a corresponding alkanesulfonate, inorganic anions, such as, for example, halide, in particular chloride, perchlorate, tetrafluoroborate, hexafluorophosphate, nitrate, hydrogensulfate, hydroxide or hydroperoxide. It may also have bridging ligands such as alkylenediamines.
  • the water-soluble builder systems serve to soften water, enhance detergency, grayness inhibition and soil dispersion. Since phosphorus and / or nitrogen-containing builders have come under criticism as detergent components for ecological reasons, water-insoluble aluminosilicates, in particular zeolite, have nowadays become established on a large scale, especially in textile detergent formulations. Together with these are often polymeric polycarboxylates, in particular copolymers based on acrylic acid and maleic acid having molecular weights in the range of 20,000 to 100,000 g / mol, used together with soda and complexing agents.
  • acylhydrazone-based bleach catalysts described above provide enhanced bleach performance and therefore improved stain removal of the detergent when used with water-soluble builder systems in place of the water-insoluble zeolites.
  • Particularly high bleaching performance is unexpectedly obtained when using soluble builder systems that are substantially free of aluminosilicate, especially zeolite, alkali citrate, and aminoalkane phosphonate, especially DTPMP.
  • the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular glycinediacetic acid, methylglycinediacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamine-N, N'-disuccinic acid and Hydroxyiminodisuccinate, ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular Aminotris (methylenphosphonklare ), 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, male
  • the relative average molecular weight (here and hereinafter: weight average) of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g / mol and 200,000 g / mol, that of the copolymers between 2,000 g / mol and 200,000 g / mol, preferably 50 000 g / mol to 120 000 g / mol, in each case based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative average molecular weight of 50,000 to 100,000.
  • Suitable, although less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight. is.
  • vinyl ethers such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene
  • terpolymers which contain two unsaturated acids and / or salts thereof as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C3-Cs-carboxylic acid and preferably from a C3-C4-monocarboxylic acid, in particular from (meth) -acrylic acid.
  • the second acidic monomer or its salt may be a derivative of a C4-Cs-dicarboxylic acid, with maleic acid being particularly preferred.
  • the third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol.
  • 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 may also be a derivative of an allylsulfonic acid substituted in the 2-position with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives is.
  • Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, from 10% by weight to 30% by weight.
  • % preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or methallyl sulfonate and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a carbohydrate
  • This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred. Particularly preferred is sucrose.
  • the use of the third monomer presumably incorporates predetermined breaking points into the polymer which are responsible for the good biodegradability of the polymer.
  • terpolymers generally have a relative average molecular weight between 1,000 g / mol and 200,000 g / mol, preferably between 200 g / mol and 50,000 g / mol.
  • Further preferred copolymers are those which contain acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • Such organic builders may be included in amounts of up to 40% by weight, more preferably up to 25% by weight and even more preferably up to 8% by weight.
  • the amount of alkali citrate may be at most 5% by weight, preferably at most 0.5% by weight, very preferably 0% by weight.
  • other water-soluble inorganic builder materials may be included.
  • the polyphosphates such as sodium triphosphate
  • these include in particular the water-soluble crystalline and / or amorphous alkali metal silicate builders.
  • Such water-soluble inorganic builder materials are preferably present in the compositions in amounts of from 1% to 20% by weight, in particular from 5% to 15% by weight.
  • the alkali metal silicates useful as builder materials preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1, 1 to 1: 12, and may be amorphous or crystalline.
  • Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of from 1: 2 to 1: 2.8.
  • Crystalline silicates which may be present alone or in a mixture with amorphous silicates are preferably crystalline phyllosilicates of the general formula Na.sub.2SixO.sub.2.sup.x + H.sub.2O.sub.2, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 is up to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • both .beta.- and .delta.-sodium disilicates are preferred.
  • amorphous alkali silicates practically anhydrous crystalline alkali metal silicates of the above general formula in which x is a number from 1, 9 to 2, 1, can be used in the compositions.
  • a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda.
  • Sodium silicates with a modulus in the range of 1.9 to 3.5 are used in another embodiment.
  • a granular compound of alkali silicate and alkali carbonate is used, as it is commercially available, for example, under the name Nabion® 15.
  • the soluble builder system consists of a) an alkali silicate having a modulus M20: SiO 2, where M is an alkali metal ion, in the range of 1: 1, 9 to 1: 3.3, b) an alkali carbonate, c) a polymeric polycarboxylate having a molecular weight of less than 10,000 g / mol, and d) a phosphonate capable of complex formation, and e) optionally an acid-acting component.
  • the soluble builder system constitutes less than 40% by weight of the total composition and the alkali product of the compositions is in the range of 7.0 to 1.1.
  • the alkali product is a quantity that allows statements about the alkalinity of detergents.
  • a pH titration of a 10 wt .-% solution of the agent in water with a pH electrode and 1, 0 molar hydrochloric acid is performed.
  • the alkali product is more than 10, it allows statements about the initial pH as well as about the buffering capacity of the solution; if it is at or below 10, then it is identical to the initial pH, statements about the buffer behavior of the solution are then not possible from the size.
  • the alkali product of the agents according to the invention is in the range from 7.0 to 1.1. Preferably, it is in the range of 8.5 to 11, 2, the agents in an especially preferred embodiment of the invention having an alkali product of 10.7 + 0.4.
  • the alkali product of the agent is determined by the composition according to the invention and can be specifically influenced in particular with the aid of the acid-acting component.
  • acidic components are all suitable for use in detergents acidic components. These may be both carboxylic acids and mineral acids or acid salts of mineral acids.
  • carboxylic acids in particular those are preferred which are also suitable as co-builders.
  • polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for environmental reasons, as well as mixtures of these.
  • these acids can be used anhydrous or in the form of their hydrates.
  • the usable mineral acids are in particular sulfuric acid, phosphoric acid, carbonic acid and hydrochloric acid, and their acid salts, to call.
  • Citric acid and / or sodium hydrogen sulfate are preferably used in the compositions according to the invention as acidic components, the sole use of citric acid being a particularly advantageous embodiment.
  • the content of the agent on the acidic component is preferably not more than 10.0% by weight; in particularly preferred embodiments, it is in the range 0, 1 and 5 wt .-%.
  • the acidic component can in principle be added at any stage of preparation of the agent.
  • it is preferred if the acid-acting component is added to the detergent subsequently, wherein the acid-acting component is present either alone or in the form of compounds with other, preferably neutral-reacting, detergent ingredients.
  • Essential for the alkali product is further the total content of builder substances. It should not be more than 40% by weight in the compositions according to the invention, in a preferred embodiment of the invention being in the range from 20 to 35% by weight.
  • Especially low Levels of builder substances are possible when the active in the wash liquor alkali carbonate is not predominantly via the direct entry of alkali carbonate, such as soda, but when the alkali carbonate of precursors that form only during the process alkali carbonate, is provided.
  • alkali metal percarbonate which liberates alkali carbonate under the influence of moisture.
  • the sodium percarbonate preferably used as a bleach in the wash liquor provides 68% of its weight as soda.
  • sodium percarbonate is used as the bleach, it provides at least 30% by weight of the total alkali carbonate active in the wash liquor, preferably even more than 50% by weight. Nevertheless, according to the invention, sodium percarbonate is not expected to be the soluble builder system since it is primarily a bleaching agent. Accordingly, in compositions containing sodium percarbonate as a bleaching agent, particularly low levels of the soluble builder system can be adjusted without detriment to washing properties. Such agents preferably contain only 10 to 25% by weight of the soluble builder.
  • the alkali carbonates used in the builder system are preferably sodium and / or potassium carbonate, with the use of sodium carbonate in particular being preferred.
  • the content of these alkali metal carbonates is preferably chosen so that the content of active in the wash liquor alkali carbonate 10 to 30 wt .-%, particularly preferably 15 to 25 wt .-%, of the total composition.
  • the alkali metal silicates used in this system are, in preferred embodiments according to the invention, amorphous sodium silicates having a modulus Na 2 O: SiO 2 of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are delay-delayed and have secondary washing properties.
  • the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous" is also understood to mean "X-ray amorphous".
  • the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays which have a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray-amorphous silicates which likewise have a dissolution delay compared with the conventional water glasses, are described, for example, in German patent application DE-A-4400024.
  • compacted / compacted amorphous silicates compounded amorphous silicates and overdried X-ray amorphous silicates.
  • Granular amorphous alkali metal silicates having bulk densities of at least 700 g / l can be prepared, for example, by a process described in the patent application WO 97/34977, which starts from the spray-drying and includes the compression of the spray-dried bead.
  • the spray-dried bead is ground and at the same time or subsequently granulated with the addition of a liquid granulation assistant, bulk densities of at least 700 g / l - up to above 1000 g / l - being set.
  • alkali silicates according to the invention can also be used in preparation forms in which they are present together with alkali carbonate.
  • crystalline, layered sodium silicates of the general formula Na 2 SixO 2 x + 1 yH 2 O wherein x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline sheet silicates are described, for example, in European Patent Application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3.
  • Na2Si205'yH20 is preferred.
  • the total content of alkali metal silicate in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymeric polycarboxylates are preferably homopolymers or copolymers which contain acrylic acid and / or maleic acid units.
  • homopolymers are particularly preferably used, again polyacrylates being preferred.
  • the polyacrylates are used in the form of sodium salts.
  • polyacrylates which preferably have a molecular weight of from 3,000 to 8,000 and more preferably from 4,000 to 5,000 g / mol have proven to be particularly suitable according to the invention.
  • the molecular weights indicated in this specification for polymeric polycarboxylates are weight-average molar masses M w , which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used.
  • the measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally higher than the molecular weights specified in this document.
  • These polymeric polycarboxylates are in the agent preferably in amounts of 0.5 to 8 wt .-%, in particular from 2 to 6.5 wt .-%, included.
  • the copolymers may also contain the copolymeric polycarboxylates usually used as co-builders, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid, having a molecular weight of between 20,000 and 70,000 g / mol.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid, have proved to be particularly suitable.
  • the polymers may also contain allylsulfonic acids, such as in EP-B-727448 allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.
  • allylsulfonic acids such as in EP-B-727448 allyloxybenzenesulfonic acid and methallylsulfonic acid
  • biodegradable polymers of more than two different monomer units for example those which, according to DE-A-43 00 772, as monomers, salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 contain as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • copolymers are those which are described in the German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • both these copolymers and the polyacrylates essential to the invention are used in the process, wherein the ratio of the polyacrylate to the acrylic acid-maleic acid copolymer in the range 2: 1 to 1: 20, preferably 1: 1 to 1: 15 , lies.
  • the content of such long-chain polycarboxylates in the compositions is at most 5 wt .-%.
  • the agents contain, in addition to the polymeric polycarboxylate having a molecular weight of less than 10,000 g / mol, no further polymer of acrylic acid, in particular no copolymer of acrylic acid with maleic acid.
  • phosphonates are in particular hydroxyalkanephosphonates.
  • the 1-hydroxyethane-1, 1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
  • aminoalkanephosphonates such as ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs, these preferably being in the form of the neutrally reacting sodium salts, eg.
  • the agents described herein in preferred embodiments are free of aminoalkane phosphonates, particularly free of DTPMP "free of" as used in this context in that the content is less than 2 Wt .-%, preferably less than 1 wt .-%, more preferably less than 0, 1 wt .-%, most preferably 0 wt .-% based on the agent.
  • HEDP is preferably used from the class of phosphonates.
  • Such phosphonates are usually included in the compositions in amounts of 0.05 to 2.0 wt .-%, preferably in amounts of 0, 1 to 1, 5 wt .-%.
  • the detergents contain substantially no aluminosilicate.
  • "Essentially no aluminosilicate” means that the content of aluminosilicates, in particular zeolite, is less than 5% by weight, based on the agent, preferably less than 3% by weight, more preferably less than 1% by weight, most preferably less than or equal to 0. If aluminosilicates are included, it is not because of their water softening effect or their carrier function that they can be present only if they are used as granulating aids, for example for powdering.
  • the detergent is characterized in that a) it contains bleach activators in amounts of up to 10 wt.%, In particular from 1.5 wt.% To 5 wt.%, And / or b) the content Aluminosilicates, in particular zeolite, less than 5% by weight, preferably less than 3% by weight, more preferably less than 1% by weight, most preferably less than 0.5% by weight, and / or c) the maximum amount of alkali citrate 5% by weight, preferably at most 0.5% by weight, very preferably 0% by weight, and / or d) the content of aminoalkane phosphonates, in particular of DTPMP, less than 2% by weight, preferably less than 1% by weight %, more preferably less than 0.1% by weight, most preferably 0% by weight, based on the agent.
  • bleach activators in amounts of up to 10 wt.%, In particular from 1.5 wt.% To 5 wt.%, And / or b) the content A
  • the detergent is characterized in that the content of aluminosilicates, in particular zeolite, less than 5 wt .-%, preferably less than 3 wt .-%, more preferably less than 1 wt .-%, most preferably less than 0.5 wt % and c) the amount of alkali citrate is at most 5% by weight, preferably at most 0.5% by weight, very preferably 0% by weight and d) the content of aminoalkane phosphonates, in particular of DTPMP, is less than 2 % By weight, preferably less than 1% by weight, more preferably less than 0.1% by weight, most preferably 0% by weight, based on the agent.
  • the content of aluminosilicates, in particular zeolite less than 5 wt .-%, preferably less than 3 wt .-%, more preferably less than 1 wt .-%, most preferably less than 0.5 wt % and c) the amount of
  • the detergent is characterized in that a) it contains bleach activators in amounts of up to 10 wt .-%, in particular from 1, 5 wt .-% to 5 wt .-% and b) the content of aluminosilicates, in particular Zeolite, less than 5% by weight, preferably less than 3% by weight, more preferably less than 1% by weight, most preferably less than 0.5% by weight and c) the amount of alkali citrate is not more than 5% by weight, preferably at most 0.5% by weight, more preferably 0% by weight and d) the content of aminoalkane phosphonates, in particular DTPMP, less than 2% by weight, preferably less than 1% by weight, more preferably less than 0, 1 wt .-%, most preferably 0 wt .-% based on the agent.
  • bleach activators in amounts of up to 10 wt .-%, in particular from 1, 5 wt .-% to 5 wt .-
  • the concentration of the compound according to formula (I) in aqueous liquor, as used for example in washing machines or dishwashers 0.5 ⁇ / ⁇ to 500 ⁇ / ⁇ , in particular 5 ⁇ / ⁇ to 100 ⁇ / ⁇ amounts.
  • the above-mentioned complex-forming metal ions are preferably not intentionally added, but they may be present from possible sources of such metal ions, which include, in particular, the tap water, the washing machine itself, adhesions to textiles, and stains on the fabrics.
  • metal ions inadvertently introduced with other detergent ingredients may also be considered.
  • Preferred peroxygen concentrations (calculated as H2O2) in the liquor are in the range from 0.001 g / l to 10 g / l, in particular from 0.1 g / l to 1 g / l and particularly preferably from 0.2 g / l to 0, 5 g / l.
  • the use according to the invention is preferably carried out at temperatures in the range from 10 ° C. to 95 ° C., in particular from 20 ° C. to 40 ° C., and particularly preferably at temperatures below 30 ° C.
  • the water hardness of the water used for preparing the aqueous liquor is preferably in the range from 0 ° dH to 21 ° dH, in particular 0 ° dH to 3 ° dH.
  • the water hardness is preferably in the range of 0 ° dH to 16 ° dH, in particular 0 ° dH to 3 ° dH, which can be achieved for example by the use of conventional builder materials or water softeners.
  • the use according to the invention is preferably carried out at pH values in the range from pH 5 to pH 12, in particular from pH 7 to pH 11.
  • the agents can also be metered low in the washing process.
  • the agent is metered so that a maximum of 45 g, preferably between 10 and 35 g, of the soluble builder system are used during the wash cycle in a household washing machine. It is ensured by the amounts of builder contained in the wash liquor that the builders perceive a sufficient water softening function.
  • the builder system can preferably be metered largely independently of the water hardness. However, in the case of large water hardnesses, it may be preferable for builder amounts in the upper half of the stated range of from 20 to 45 g, in particular from 25 to 35 g, to be metered in the wash cycle.
  • the use according to the invention is preferably carried out by allowing a peroxygen compound and a detergent containing an acylhydrazone of the general formula (I) and a water-soluble builder system to act on a contaminated textile in the course of a machine or hand washing operation.
  • the use according to the invention can be particularly easily achieved by the use of a detergent, the peroxygen compound, water-soluble builder system and a compound of formula (I) or a containing by complexing with a said transition metal ion from this accessible bleach catalyst, be realized in the laundry of textiles requiring cleaning.
  • the peroxygen compound and / or the compound of formula (I) and / or a complex obtainable therefrom and / or the water-soluble builder system can also be added separately to a wash liquor which has a detergent without the particular ingredient mentioned.
  • Another object of the invention is a detergent containing a peroxygen bleaching agent and a combination of water-soluble builder system and a compound of formula (I).
  • the compound of formula (I) may also be present in the form of a bleach catalyst obtainable by complexation with a transition metal ion thereof from said agent.
  • the molar ratio of said transition metal or the sum of said transition metals to the compound according to formula (I) is preferably in the range of 0.001: 1 to 2: 1, in particular 0.01: 1 to 1: 1.
  • Agents are contained in these 0.05 wt .-% to 1 wt .-%, in particular 0.1 wt .-% to 0.5 wt .-% of bleach-enhancing complex having a ligand according to formula (I) included.
  • Preferred transition metal is Mn.
  • peroxygen compounds contained in the agents are in particular organic peracids or pers acid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperoxododecanedioic acid, other peroxo acids or peroxyacid salts, such as alkali metal or peroxodisulfates or caroates, or diacyl peroxides or tetraacyldiperoxides, hydrogen peroxide and under the washing conditions, hydrogen peroxide-releasing substances, such as alkali metal perborates, alkali metal peroxides, alkali metal peracidates and urea perhydrate, into consideration.
  • organic peracids or pers acid salts of organic acids such as phthalimidopercaproic acid, perbenzoic acid or salts of diperoxododecanedioic acid, other peroxo acids or peroxyacid salts, such as alkali metal or peroxodisulfates or
  • Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate.
  • solid peroxygen compounds ie an oxidase and its substrate.
  • solid peroxygen compounds can be used in the form of powders or granules, which can also be enveloped in a manner known in principle.
  • peroxygen compounds are present in the compositions in amounts of up to 50% by weight, more preferably from 2% to 45% and more preferably from 5% to 20% by weight.
  • a conventional bleach activator is used together with the acyl hydrazone of the general formula (I), the general formula (II) and in particular the formula (III).
  • bleach activators are preferably present in amounts of up to 10 wt .-%, in particular from 1, 5 wt .-% to 5 wt .-%.
  • Compounds which can be added under perhydrolysis conditions to give peroxocarboxylic acid are, in particular, compounds which, under perhydrolysis conditions, optionally substituted perbenzoic acid and / or aliphatic peroxycarboxylic acids having 1 to 12 C atoms, in particular 2 to 4 C atoms, are used alone or in mixtures.
  • Suitable are bleach activators which carry O- and / or N-acyl groups, in particular of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT ), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates or carboxylates or the sulfonic or carboxylic acids of these, in particular nonanoyl or isononanoyl or lauroylbenzenesulfonate (NOBS or iso-NOBS or LOBS) or decanoyloxybenzoate (DOBA) whose formal carbonic acid ester derivatives such as 4- (2-decanoyloxyethoxycarbonyloxy)
  • bleach-activating compounds such as, for example, nitriles, from which perimides acids are formed under perhydrolysis conditions.
  • nitriles include in particular aminoacetonitrile derivatives with quaternized nitrogen atom according to the formula
  • R 2 and R 3 are independently selected from -CH 2 -N-CN, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3, -CH 2 -OH, -CH 2 -CH 2 OH, -CH (OH) -
  • the bleach activators may have been coated or granulated in known manner with coating substances, granulated tetraacetylethylenediamine having average particle sizes of 0.01 mm to 0.8 mm, granulated by means of carboxymethylcellulose 1, 5-diacetyl-2,4-dioxo-hexahydro-1, 3,5-triazine, and / or formulated in particulate form Trialkylammoniumacetonitrile is particularly preferred.
  • customary bleach-activating 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 and its substituted derivatives such as 1, 4,7-trimethyl-1, 4,7-triazacyclononane, 1, 5,9-triazacyclododecane and its substituted derivatives such as 1, 5,9- Trimethyl-1, 5,9-triazacyclododecane 1, 4,8,1,1-tetraazacyclotetradecane and its substituted derivatives such as 5,5J, 12,12,14-hexamethyl-1,4,8,1-tetraazacyclote
  • the inorganic neutral ligands include in particular ammonia and water. If not all coordination sites of the transition metal central atom are occupied by neutral ligands, the complex contains further, preferably anionic and among these in particular mono- or bidentate ligands. These include in particular the halides such as fluoride, chloride, bromide and iodide, and the (NO 2) - group, that is a nitro ligand or a nitrito ligand.
  • the (NO 2) - group may also be chelated to a transition metal or it may be asymmetric or two transition metal atoms -0-bridging.
  • 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 ⁇ ( ⁇ ) 2 ( ⁇ -O) 3 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) di-hexafluorophosphate, [N, N'-bis [(2 -hydroxy-5-vinylphenyl) -methylene] -1,2-diaminocyclohexane] -manganese (III) chloride, [ ⁇ , ⁇ '-bis [(2-hydroxy-5-nitrophenyl) methylene] -1, 2 diaminocyclohexane] manganese (III) acetate, [N, N'-bis [(2-hydroxyphenyl) methylene] -1, 2-phenylenediamine] manganese (III) acetate, [N, N'- bis [(2-hydroxyphenyl) - methylene] -1,2-diaminocyclohexane] manganese (III) chloride, [N, N'-bis [(2-hydroxyphenyl)
  • the water-soluble builder systems are included in the compositions of the invention in the amounts disclosed above within the scope of the use.
  • Detergents which may be in the form of homogeneous solutions or suspensions, especially in powdered solids, in densified particle form, can in principle all known and known except for the invention to be used combination of water-soluble builder system and compound of formula (I) and optionally the said bleach activators and catalysts contain usual ingredients in such agents.
  • the agents may, in particular, be surface-active surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, special effect polymers such as soil release polymers, dye transfer inhibitors, grayness inhibitors, wrinkle-reducing polymeric agents and form-retaining polymeric agents, and other adjuvants such as optical brighteners , Foam regulators, dyes and fragrances.
  • An agent may be used to further enhance the disinfecting effect, for example against specific germs, in addition conventional antimicrobial agents such as alcohols, aldehydes, acids, carboxylic acid esters, acid amides, phenols and phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, bound to organic frameworks O-acetates and O.
  • conventional antimicrobial agents such as alcohols, aldehydes, acids, carboxylic acid esters, acid amides, phenols and phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, bound to organic frameworks O-acetates and O.
  • benzamidines isothiazolines, phthalimide derivatives, pyridine derivatives, amines, quaternary ammonium compounds, guanidines, amphoteric compounds, quinolines, benzimidazoles, IPBC, dithiocarbamates, metals and metal compounds such as silver and silver salts, halogens such as chlorine, iodine and theirs Compounds, other oxidizing agents and inorganic nitrogen compounds.
  • Such antimicrobial additives are preferably present in amounts of up to 10 wt .-%, in particular from 0.01 wt .-% to 5 wt .-%, each based on the total agent included; in a preferred embodiment, however, they are free of such additional disinfecting agents.
  • the agents may contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic and / or amphoteric surfactants may be included.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • Suitable alkylbenzenesulfonates are preferably selected from linear or branched alkylbenzenesulfonates of the formula
  • a particularly preferred representative is sodium dodecylbenzylsulfonate.
  • Alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12-18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those monoesters secondary Alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the Ci2-Ci6-alkyl sulfates and Ci2-Ci5-alkyl sulfates and C14-C15-alkyl sulfates are preferred.
  • sulfuric acid monoesters of straight-chain or branched C7-2i alcohols ethoxylated with from 1 to 6 moles of ethylene oxide such as 2-methyl-branched C9-11 alcohols having on average 3.5 moles of ethylene oxide (EO) or C12-C18 fatty alcohols with 1 up to 4 EO, are suitable.
  • Suitable alkyl ether sulfates are, for example, compounds of the formula
  • R is a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical.
  • Preferred radicals R are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with even number of carbon atoms are preferred.
  • radicals R are derived from C 12-18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C 10 -C 20 oxo alcohols.
  • AO represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety.
  • EO ethylene oxide
  • PO propylene oxide
  • the index n stands for an integer from 1 to 50, preferably from 1 to 20 and especially from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7 or 8.
  • X stands for a monovalent cation or the nth part of an n-valent cation, the alkali metal ions are preferred, and Na + or K + including Na, with Na + being extremely preferred.
  • Other cations X + can be selected from NhV,
  • the alkyl ether sulfate may be selected from fatty alcohol ether sulfates of the formula
  • ethoxylation represents a statistical average that may be an integer or a fractional number for a particular product.
  • the indicated degrees of alkoxylation represent statistical averages, which may be an integer or a fractional number for a particular product.
  • Preferred alkoxylates / ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • anionic surfactants are particularly soaps into consideration.
  • Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium, potassium or magnesium salts, in particular in the form of the sodium salts.
  • anionic surfactants are the freedom from formulation no conditions to be observed in the way.
  • Preferred anionic surfactants to be used are the alkylbenzenesulfonates and fatty alcohol sulfates, in particular the alkylbenzenesulfonates.
  • Anionic surfactants including the soaps i. in particular alkylbenzenesulfonates, alkyl ether sulfates and soaps, are preferably present in the detergent at a certain proportion by weight, namely from 5 to 25% by weight, based on the total weight of the detergent formulation. Preference is given to amounts of from 7 to 20% by weight of anionic surfactants, based on the total weight of the detergent formulation. Regardless of whether the detergent contains one or more of the anionic surfactants, the amounts given refer to the total amount of all anionic surfactants contained in the detergent.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates having linear radicals of alcohols of native origin having 12 to 18 carbon atoms, e.g. from coconut, palm, tallow or oleyl alcohol, and on average from 2 to 8 EO per mole of alcohol.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 7 -n-alcohol with 7 EO, cis-is alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-14 alcohol with 3 EO and Ci2-is-alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • 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 used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG).
  • APG alkyl polyglycosides
  • Usable alkylpolyglycosides satisfy the general formula RO (G) z , in which R is a linear or branched, especially in the 2-position methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the glycosidation degree z is between 1, 0 and 4.0, preferably between 1, 0 and 2.0 and in particular between 1, 1 and 1, 4.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • Such surfactants are present in detergents in proportions of preferably from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight.
  • Suitable enzymes in the detergents are, in particular, those from the class of proteases, cutinases, amylases, lipases, pullulanases, xylanases, hemicellulases, cellulases, peroxidases and oxidases or mixtures thereof, the use of protease, amylase, lipases and / or or cellulase is particularly preferred.
  • the proportion is preferably 0.2 wt .-% to 1, 5 wt .-%, in particular 0.5 wt .-% to 1 wt .-%.
  • the enzymes can be adsorbed in a customary manner on carriers and / or embedded in coating substances or incorporated as concentrated, as anhydrous liquid formulations.
  • Suitable gravel inhibitors or soil release agents are cellulose ethers, such as carboxymethylcellulose, methylcellulose, hydroxyalkylcelluloses and cellulose mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose and methylcarboxymethylcellulose.
  • cellulose ethers such as carboxymethylcellulose, methylcellulose, hydroxyalkylcelluloses and cellulose mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose and methylcarboxymethylcellulose.
  • sodium carboxymethylcellulose and mixtures thereof with methylcellulose are used.
  • Commonly used soil release agents include copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units.
  • the proportion of graying inhibitors and / or soil-release active ingredients in the compositions is generally not more than 2% by weight and is preferably from 0.5% by weight to 1.5% by weight.
  • detergents may contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts.
  • salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazin-6-yl-amino) -stilbene-2,2'-disulphonic acid or similarly constructed compounds which are suitable instead of the morpholino group carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group.
  • brighteners of the type substituted 4,4'-distyryl-diphenyl for example 4,4'-bis- (4-chloro-3-sulfostyryl) -diphenyl.
  • mixtures of brighteners can be used.
  • polyamide fibers are particularly well brighteners of the type of 1, 3-diaryl-2-pyrazolines, for example 1- (p-sulfoamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline and similarly structured compounds.
  • the content of the composition in optical brighteners or brightener mixtures is generally not more than 1 wt .-%, and preferably in the range of 0.05 wt .-% to 0.5 wt .-%.
  • the customary foam regulators which can be used in detergents include, for example, polysiloxane-silica mixtures, the finely divided silica contained therein preferably being silanated or otherwise rendered hydrophobic.
  • the polysiloxanes can consist of both linear compounds as well as crosslinked polysiloxane resins and mixtures thereof.
  • Further antifoams are paraffin hydrocarbons, in particular microparaffins and paraffin waxes whose melting point is above 40 ° C., saturated fatty acids or soaps having in particular 20 to 22 carbon atoms, for example sodium behenate, and alkali metal salts of phosphoric mono- and / or dialkyl esters in which the alkyl chains each having 12 to 22 carbon atoms.
  • the proportion of foam regulators may preferably be from 0.2% by weight to 2% by weight.
  • any of the detergents described herein may be any method known in the art.
  • the preparation of solid compositions can be carried out in a manner known in principle, for example by spray-drying or granulation, with thermally sensitive ingredients optionally being added separately later.
  • compositions are preferably in the form of pulverulent, granular or tablet-like preparations which are prepared in a manner known per se, for example by mixing, granulating, roller compacting and / or spray-drying the thermally stable components and admixing the more sensitive components, in particular enzymes, bleaches and bleach-activating agents Active ingredients are expected to be produced.
  • a process comprising an extrusion step is preferred.
  • a tablet thus produced has a weight of 15 g to 40 g, in particular from 20 g to 30 g, with a diameter of 35 mm to 40 mm.
  • Another object of the invention is a method for washing textiles in which an agent according to the invention is used.
  • This agent is preferably metered so that during the wash cycle in a household washing machine a maximum of 45 g, preferably between 10 and 35 g, of the soluble builder system are used.
  • the builder system can preferably be metered largely independently of the water hardness.
  • processes for cleaning textiles are generally distinguished by the fact that cleaning-active substances are applied to the items to be cleaned in one or more process steps and washed off after the action time, or that the items to be cleaned are otherwise treated with a detergent or a solution of this agent.
  • temperatures of up to 95 ° C or less, 90 ° C or less, 60 ° C or less, 50 ° C or less, 40 ° C or less, 30 ° C or less, or 20 ° C or less used. These temperature data refer to the temperatures used in the washing steps.
  • the uses, compositions and methods described above in connection with detergents are also applicable to hard surface cleaners.
  • the invention thus also encompasses the use of the described combinations for improving the cleaning performance of hard surface cleaners, corresponding cleaning agents and methods in which such cleaners are used.
  • all facts, objects and embodiments described for the uses and detergents are also applicable to the washing processes and vice versa.
  • Table 1 shows a powder detergent B according to the invention in comparison with a powder detergent A not according to the invention (all data in% by weight, unless stated otherwise):
  • Table 2 The values given (Table 2) are mean values of 6 determinations. The soiled textiles were bought or self-made. The differences between the remission values and the standard detergent are shown.

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Abstract

La présente invention concerne l'utilisation d'une combinaison de systèmes d'adjuvants hydrosolubles et de certaines acylhydrazones pour améliorer l'élimination des taches, notamment des taches blanchissables hydrophiles, comme les taches de vin rouge, de thé, de fruits rouges, ou de boissons et d'aliments à base de ceux-ci, ou qui contiennent des colorants correspondants à ceux-ci, par des détergents, lors du lavage de textiles ou du nettoyage de surfaces dures. La présente invention concerne également des détergents qui contiennent une combinaison de ce type.
EP16712050.0A 2015-03-31 2016-03-30 Composition de détergent à élimination améliorée des taches Ceased EP3277786A1 (fr)

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DE102015205799.2A DE102015205799A1 (de) 2015-03-31 2015-03-31 Waschmittelzusammensetzung mit verbesserter Fleckentfernung
PCT/EP2016/056851 WO2016156351A1 (fr) 2015-03-31 2016-03-30 Composition de détergent à élimination améliorée des taches

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DE4400024A1 (de) 1994-01-03 1995-07-06 Henkel Kgaa Silikatische Builder und ihre Verwendung in Wasch- und Reinigungsmitteln sowie Mehrstoffgemische für den Einsatz auf diesem Sachgebiet
DE4417734A1 (de) 1994-05-20 1995-11-23 Degussa Polycarboxylate
US5547612A (en) 1995-02-17 1996-08-20 National Starch And Chemical Investment Holding Corporation Compositions of water soluble polymers containing allyloxybenzenesulfonic acid monomer and methallyl sulfonic acid monomer and methods for use in aqueous systems
DE19545727A1 (de) * 1995-12-07 1997-06-12 Henkel Kgaa Alkalipercarbonathaltiges Waschmittel
DE19611012A1 (de) 1996-03-21 1997-09-25 Henkel Kgaa Verfahren zur Herstellung von granularen Silikaten mit hohem Schüttgewicht
AU2003292165A1 (en) * 2002-12-20 2004-07-22 Henkel Kommanditgesellschaft Auf Aktien Bleach-containing washing or cleaning agents
WO2004069978A1 (fr) * 2003-02-10 2004-08-19 Henkel Kommanditgesellschaft Auf Aktien Produit de lavage ou de nettoyage contenant un agent de blanchiment ainsi qu'un systeme adjuvant hydrosoluble et un derive cellulosique a pouvoir nettoyant
EP2651907B1 (fr) * 2010-12-13 2014-10-01 Basf Se Catalyseurs de blanchiment
DE102012200333A1 (de) 2012-01-11 2013-07-11 Henkel Ag & Co. Kgaa Acylhydrazone als bleichverstärkende Wirkstoffe
DE102012219359A1 (de) * 2012-10-23 2014-04-24 Henkel Ag & Co. Kgaa Wasch- und Reinigungsmittel mit verbesserter Hygieneleistung
DE102013215810A1 (de) * 2013-08-09 2015-02-12 Henkel Ag & Co. Kgaa Waschmittel mit erhöhter Primärwaschkraft

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