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EP1572851B1 - Produits de lavage et de nettoyage contenant un agent de blanchiment - Google Patents

Produits de lavage et de nettoyage contenant un agent de blanchiment Download PDF

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Publication number
EP1572851B1
EP1572851B1 EP03767718A EP03767718A EP1572851B1 EP 1572851 B1 EP1572851 B1 EP 1572851B1 EP 03767718 A EP03767718 A EP 03767718A EP 03767718 A EP03767718 A EP 03767718A EP 1572851 B1 EP1572851 B1 EP 1572851B1
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EP
European Patent Office
Prior art keywords
weight
alkali metal
composition according
acid
silicate
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.)
Revoked
Application number
EP03767718A
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German (de)
English (en)
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EP1572851A1 (fr
Inventor
Horst-Dieter Speckmann
Joerg Poethkow
Heike Schirmer-Ditze
Gerhard Blasey
Birgit Middelhauve
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority claimed from DE10320196A external-priority patent/DE10320196A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1572851A1 publication Critical patent/EP1572851A1/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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0013—Liquid compositions with insoluble particles in suspension
    • 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
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • 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
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D3/3942—Inorganic per-compounds

Definitions

  • the present invention relates to particulate detergents or cleaners which have only water-soluble constituents as builder component and contain particularly coated alkali metal percarbonate particles.
  • Washing and cleaning agents normally contain, in addition to the surfactants which are indispensable for the washing or cleaning performance, so-called builder substances which have the task of supporting the performance of the surfactants by eliminating hardness formers, ie essentially calcium and magnesium ions, from the wash liquor should not interact negatively with the surfactants.
  • builder substances which have the task of supporting the performance of the surfactants by eliminating hardness formers, ie essentially calcium and magnesium ions, from the wash liquor should not interact negatively with the surfactants.
  • Polyphosphates in particular sodium triphosphate, have been used very successfully for this purpose in the past, but because of the known water-reutrophizing effect, they have not been used for decades or can only be used with restrictions.
  • zeolite Na-A Another known example of such primary detergency-improving builders is zeolite Na-A, which is known to be capable of forming so stable complexes with especially calcium ions that their reaction with water-hard-forming anions, especially carbonate, to form insoluble compounds is suppressed.
  • builders particularly in laundry detergents, are expected to prevent the redeposition of soil detached from the fiber or generally from the surface to be cleaned, as well as the formation of insoluble compounds on the cleaned fabric or surface due to the reaction of water hardness cations with water hardness forming anions.
  • co-builders usually polymeric polycarboxylates, which in addition to their contribution to the secondary washing ability advantageously also a Have complexing effect against the water hardness-forming cations.
  • detergents In addition to the indispensable active ingredients such as surfactants and builder materials, detergents generally contain further constituents, which can be summarized under the term washing aids and which comprise such different active ingredient groups as foam regulators, grayness inhibitors, bleaches, enzymes and dye transfer inhibitors.
  • washing aids which comprise such different active ingredient groups as foam regulators, grayness inhibitors, bleaches, enzymes and dye transfer inhibitors.
  • the bleaching agents are of particular importance.
  • excipients include substances which assist in detergency the surfactant performance by the oxidative degradation of soils located on the textile or those that are in the fleet after detachment from the textile. The same applies mutatis mutandis to cleaners for hard surfaces.
  • inorganic peroxygen compounds particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water to release hydrogen peroxide or so-called active oxygen, such as sodium perborate and sodium carbonate perhydrate
  • active oxygen such as sodium perborate and sodium carbonate perhydrate
  • the alkali metal percarbonate must normally against Loss of active oxygen to be stabilized.
  • An essential principle for stabilization is to surround the alkali metal percarbonate particles with a shell which may be mono- or multilayered. Each shell layer may contain one or more inorganic and / or organic shell components.
  • the presence of a shell usually causes a change in the release characteristics of the alkali metal percarbonate.
  • the good solubility in water of non-coated alkali metal percarbonate may be detrimental to their presence in enzyme-containing detergents or cleaners, since relatively high concentrations of active oxygen are already available shortly after the start of the washing or cleaning process, which has the effect of a number of enzymes, including also proteases, can affect.
  • This impairment need not necessarily be due to the oxidative degradation ("denaturation") of the enzymatic agent, but may also be due to some soils, such as blood, being actually removed by the enzyme by the action of the bleaching agent in one of the enzymes Less well attackable form are transferred. It is therefore desirable to achieve a delayed release of the active oxygen by the enclosure of the alkali metal percarbonate.
  • the coating of the alkali metal percarbonate particles described in these documents contains, in addition to magnesium sulfate or a magnesium carboxylate, a salt from the series of alkali metal carbonates, bicarbonates and sulfates and, as a third component, an alkali metal silicate, wherein said coating components can be arranged in one or more layers .
  • a salt from the series of alkali metal carbonates, bicarbonates and sulfates and, as a third component, an alkali metal silicate, wherein said coating components can be arranged in one or more layers
  • European patent application EP 0 623 533 it follows that the rate of dissolution of coated sodium percarbonate particles decreases with increasing amount of sodium silicate.
  • International Patent Application WO 97/19890 teaches that sodium percarbonate having a single shell layer of substantially sodium sulfate has at least sufficient active oxygen stability when the sodium percarbonate core material was produced by fluidized bed spray granulation. The dense grain structure, however, only led to a slightly
  • European patent application EP 0 922 575 teaches the possibility of prolonging the dissolution time of sodium percarbonate by the presence of alkali metal silicate: from 0.5% to 30% by weight.
  • Alkali silicate with modulus greater than 3 and smaller 5 either mixed with sodium percarbonate or applied in the form of a coating layer on this.
  • the cladding layer consists of 9% by weight of sodium silicate.
  • carboxylic acids or hydroxycarboxylic acids in one or more cladding layers.
  • other known stabilizers from the series magnesium sulfate, sodium sulfate, sodium carbonate and sodium bicarbonate may be present in the cladding layer.
  • the sodium percarbonate particles thus coated are used in combination with enzymes in particular for washing textiles or dishwashing, in which case only zeolite or sodium tripolyphosphate-containing agents are specifically disclosed.
  • laundry detergents which comprise a cationic ester surfactant and an alkalinity system, which may also be sodium percarbonate
  • an alkalinity system which may also be sodium percarbonate
  • a sheath with sodium silicate having a modulus in the range from 1.6 to 3.4, in particular 2.8 is considered, wherein instead of the sodium silicate and magnesium silicate is referred to as suitable.
  • the so-coated, referred to as "slow release particles" sodium percarbonate particles are used, partially together with sodium perborate, in zeolite and / or sodium tripolyphosphate-containing agents.
  • US Pat. No. 5,902,682 discloses detergents containing sodium percarbonate particles coated with a combination of sodium carbonate, a magnesium salt and an alkali metal silicate.
  • the sodium percarbonate particles are used in compositions containing organic and / or inorganic builders.
  • alkali metal percarbonate particles which comprise a coating layer containing alkali metal silicate develops particularly well when these alkali metal percarbonate particles are used in detergents or cleaning agents which are free of water-insoluble builder material, ie contain only water-soluble builders. wherein phosphate builders as outlined above due to environmental concerns are not eligible.
  • the invention therefore relates to a particulate bleach and builder-containing detergent or cleaner comprising (A) a phosphate-free water-soluble builder block and (B) alkali metal percarbonate particles which comprise a coating layer containing alkali metal silicate.
  • the agent may contain any other ingredients commonly used in detergents or cleansers unless they unduly interact negatively with or in any of these.
  • builder block By using the term “builder block” is to be expressed, however, that the means do not contain other builders than those which are water-soluble and phosphate-free, that is all builders contained in the agent are summarized in the so-characterized "block", possibly the Amounts of substances are excluded, which may be commercially available as impurities or stabilizing additives in small amounts in the other ingredients of the funds.
  • no additional bleaching agent is included in addition to the said coated alkali metal percarbonate, although this is possible if desired. Preference is given to means in which the proportion of Alkalipercarbonatpumble 6 wt .-% to 30 wt .-%, in particular 10 wt .-% to 25 wt .-% is.
  • Preferred alkali metal herein is sodium, as well as any other part of the present specification, although lithium, potassium and rubidium salts may be used if desired.
  • the coated alkali metal percarbonate particles contained in the compositions according to the invention have an alkali percarbonate core, which may have been produced by any preparation process and may also contain per se known stabilizers, such as magnesium salts, silicates and phosphates.
  • the manufacturing processes customary in practice are, in particular, so-called crystallization processes and fluidized-bed spray granulation processes. In the crystallization process, hydrogen peroxide and alkali carbonate are reacted in aqueous phase to alkali metal percarbonate and the latter is separated from the aqueous mother liquor after crystallization.
  • alkali percarbonate can also be produced by a process comprising contacting solid alkali carbonate or a hydrate thereof with an aqueous solution of hydrogen peroxide and drying, core of the alkali metal percarbonate particles.
  • the alkali metal percarbonate particles present in the agents according to the invention preferably have at least two coating layers, wherein an innermost layer contains at least one hydrate-forming inorganic salt and an outer layer alkali silicate.
  • the outer alkali silicate containing cladding layer may either be the outermost cladding layer of a cladding comprising at least two layers or a cladding layer which is not the innermost one, directly on the alkali percarbonate, which in turn may be superposed by one or more layers.
  • This at least partial penetration results from the fact that during the coating of alkali metal percarbonate particles, which have an innermost coating layer, this is at least superficially dissolved when a solution containing a coating component or the coating components of a second coating layer is sprayed on.
  • the enveloping of the alkali metal percarbonate can be done in a conventional manner.
  • the particles to be coated are contacted with a solution containing one or more shell components as uniformly as possible once or several times and are dried simultaneously or subsequently.
  • the contacting may take place on a granulating dish or in a mixer, such as a tumbling mixer.
  • Coating is particularly advantageously carried out by fluidized-bed etching, in which case a first solution containing the cull component is first or components Kir.Aus Struktur an innermost layer, and then a second solution containing the Küllkomponente or components to form an outer layer, sprayed on the in a fluidized bed alkali metal percarbonate or on the coated with a layer or more layers Alkalipercarbonat and simultaneously the fluidized bed gas is dried.
  • Fluidized bed gas may be any gas, in particular air, air directly heated with a combustion gas having a CO 2 content of, for example, from 0.1 to about 15%, pure CO 2 , nitrogen and inert gases.
  • the coated alkali metal percarbonate used in a preferred embodiment in compositions according to the invention contains in the innermost shell layer at least one inorganic salt capable of hydrate formation.
  • the innermost shell layer may also contain other stabilizing inorganic salts and / or organic compounds, such as alkali metal salts of carboxylic acids or hydroxycarboxylic acids.
  • the innermost shell layer contains one or more salts from the series of alkali metal sulphates, alkali metal carbonates, alkali metal bicarbonates, alkali metal borates and alkali metal perborates.
  • the innermost layer may also contain magnesium sulfate, alone or in admixture with one or more of the aforementioned salts.
  • the innermost shell layer consists essentially of alkali metal sulphate, which may also be partly in hydrated form.
  • the term "substantially” means that at least in the boundary layer between the Alkalipercarbonatkern and the innermost layer and alkali metal bicarbonate or a double salt of alkali metal bicarbonate, such as sesquicarbonate or Wegscheider salt may be included.
  • the innermost layer of the coated particle preferably makes up 2% by weight 20 wt .-%, in particular 3 wt .-% to 10 wt .-% and particularly preferably 4 wt .-% to 8 wt .-%, each based on the coated alkali metal, from.
  • the stated amount of sheath is the shell in hydrate-free form.
  • the amount of coating can increase by storage in a humid atmosphere by hydrate formation.
  • the cladding layer containing the alkali silicate which may be directly on the alkali percarbonate core, but is preferably disposed as an outer layer, in particular as a second layer on the innermost cladding layer set forth above, preferably accounts for 0.2% to 3% by weight. , in particular 0.3 wt .-% to less than 1 wt .-% of the coated particle.
  • a further reduction of the amount of alkali metal silicate is possible in principle, but then the dissolution-increasing effect is less. In the same way, an increase in the amount of alkali metal silicate is possible if a particularly long dissolution time is desired.
  • the alkali metal silicate preferably has a modulus of greater than 2.5, in particular in the range from 3 to 5, and particularly preferably from 3.2 to 4.2.
  • the modulus is the molar ratio of SiO 2 to M 2 O, where M is the alkali metal.
  • agents according to the invention contain a water-soluble builder block.
  • water-soluble is to be understood as meaning that the builder block dissolves without leaving any residue at least 3 g / l, in particular at least 6 g / l, in water of pH 7 at room temperature.
  • the builder block is at the concentration determined by the amount of use of it containing detergent at the usual washing conditions, residue-free soluble.
  • the phosphate-free water-soluble builder block contains at least 2 of components b), c) and d) in amounts greater than 0% by weight.
  • component a in a preferred embodiment of the composition according to the invention, 15% by weight to 25% by weight of alkali carbonate, which may at least partly be replaced by alkali metal hydrogencarbonate, and up to 5% by weight, in particular 0.5% by weight. % to 2.5% by weight of citric acid and / or alkali citrate.
  • inventive compositions are as component a) 5 wt .-% to 25 wt .-%, in particular 5 wt .-% to 15 wt .-% citric acid and / or alkali citrate and up to 5 wt .-%, in particular 1 wt .-% to 5 wt .-% alkali carbonate, which may be at least partially replaced by alkali metal bicarbonate included. If both alkali metal carbonate and alkali metal bicarbonate are present, the component comprises a) alkali carbonate and alkali metal bicarbonate, preferably in a weight ratio of 10: 1 to 1: 1.
  • component b) in a preferred embodiment of the composition according to the invention, 1% by weight to 5% by weight of alkali metal silicate with a modulus in the range from 1.8 to 2.5 are contained.
  • agents according to the invention contain from 0.05% by weight to 1% by weight of phosphonic acid and / or alkali metal phosphonate.
  • Phosphonic acids are also understood as meaning optionally substituted alkylphosphonic acids, which may also have a plurality of phosphonic acid groups (so-called polyphosphonic acids).
  • They are preferably selected from the hydroxy and / or aminoalkylphosphonic acids and / or their alkali metal salts, for example dimethylaminomethane diphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethanediphosphonic acid, 1-hydroxyethane-1 , 1-diphosphonic acid, amino-tris (methylenephosphonic acid), N, N, N ', N'-ethylenediaminetetrakis (methylenephosphonic acid) and the acylated derivatives of phosphorous acid described in the German patent DE 11 07 207, which are also used in any mixtures can.
  • dimethylaminomethane diphosphonic acid 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethanediphosphonic acid, 1-hydroxyethane-1 , 1-diphosphonic acid, amino-tris (methylenephosphonic acid), N, N, N
  • component d) in a preferred embodiment of the composition according to the invention 1.5 wt .-% to 5 wt .-% polymeric polycarboxylate, in particular selected from the polymerization or copolymerization of acrylic acid, methacrylic acid and / or maleic acid.
  • polymeric polycarboxylate in particular selected from the polymerization or copolymerization of acrylic acid, methacrylic acid and / or maleic acid.
  • homopolymers of acrylic acid and among these in turn those with an average molecular weight in the range of 5,000 D to 15,000 D (PA standard) are particularly preferred.
  • the component of the bleach activators additionally present in preferred embodiments comprises the commonly used N- or O-acyl compounds, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulphurylamides and cyanurates, also carboxylic anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyl and - isononanoyl-phenolsulfonat, and acylated sugar derivatives, in particular pentaacetylglucose, and cationic nitrile derivatives such as trimethylammoniumacetonitrile salts.
  • N- or O-acyl compounds for example polyacylated alkylenediamines, in particular
  • the bleach activators may have been coated or granulated in known manner with encapsulating substances, tetraacetylethylenediamine granulated by means of carboxymethylcellulose having mean particle sizes of from 0.01 mm to 0.8 mm, as described, for example, in US Pat granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, as can be prepared according to the process described in German Patent DD 255,884 , and / or according to the in particulate form described in International Patent Applications WO 00/50553, WO 00/50556, WO 02/12425, WO 02/12426 or WO 02/26927 described method trialkylammoniumacetonitrile is particularly preferred.
  • such bleach activators are preferably present in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the
  • an agent according to the invention contains nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or fatty acid amides and mixtures thereof , in particular in an amount in the range of 2 wt .-% to 25 wt .-%.
  • Suitable nonionic surfactants include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched-chain alcohols having 10 to 22 C atoms, preferably 12 to 18 C atoms.
  • the degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides.
  • Particularly suitable are the derivatives of fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used for the preparation of usable alkoxylates.
  • alkoxylates in particular the ethoxylates, primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof.
  • suitable alkoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the said alcohols with respect to the alkyl part usable.
  • the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters as can be prepared according to the process disclosed in International Patent Application WO 90/13533, and fatty acid polyhydroxyamides, as prepared according to the processes of US Pat. Nos.
  • alkylpolyglycosides which are suitable for incorporation in the compositions according to the invention are compounds of the general formula (G) n -OR 12 , in which R 12 is an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10 mean.
  • R 12 is an alkyl or alkenyl radical having 8 to 22 C atoms
  • G is a glycose unit
  • n is a number between 1 and 10 mean.
  • Such compounds and their preparation are described, for example, in European patent applications EP 92 355, EP 301 298, EP 357 969 and EP 362 671 or US Pat. No. 3,547,828.
  • the glycoside component (G) n are oligomers or polymers of naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, Include xylose and lyxose.
  • the oligomers consisting of such glycosidically linked monomers are characterized not only by the nature of the sugars contained in them by their number, the so-called Oligomermaschinesgrad.
  • the degree of oligomerization n assumes as the value to be determined analytically generally broken numerical values; it is between 1 and 10, with the glycosides preferably used below a value of 1.5, in particular between 1.2 and 1.4.
  • Preferred monomer building block is glucose because of its good availability.
  • the agents may instead or in addition further nonionic, zwitterionic, cationic or anionic surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, such as alkylbenzenesulfonates, in amounts of preferably not more than 20 wt .-%, in particular of 0.1 wt. -% to 18 wt .-%, each based on the total agent included.
  • nonionic, zwitterionic, cationic or anionic surfactants preferably synthetic anionic surfactants of the sulfate or sulfonate type, such as alkylbenzenesulfonates
  • Suitable synthetic anionic surfactants which are particularly suitable for use in the compositions are the alkyl and / or alkenyl sulfates having 8 to 22 C atoms which carry an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation. Preference is given to the derivatives of the fatty alcohols having in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols.
  • the alkyl and alkenyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases.
  • Sulfur-type surfactants which can be used also include the sulfated alkoxylation products of the alcohols mentioned, known as ether sulfates.
  • ether sulfates preferably contain from 2 to 30, in particular from 4 to 10, ethylene glycol groups per molecule.
  • Suitable anionic surfactants of the sulfonate type include the ⁇ -sulfoesters obtainable by reaction of fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those of fatty acids having 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation, as well as the formal saponification resulting from these sulfo fatty acids.
  • a further preferred embodiment of such agents comprises the presence of sulfate and / or sulfonate synthetic anionic surfactant, in particular fatty alkyl sulfate, fatty alkyl ether sulfate, sulfo fatty acid ester and / or sulfo fatty acid salt, in particular in an amount in the range of 2% by weight to 25% by weight.
  • the anionic surfactant is preferably selected from the alkyl or alkenyl sulfates and / or the alkyl or alkenyl ether sulfates in which the alkyl or alkenyl group has 8 to 22, in particular 12 to 18, carbon atoms. These are usually not individual substances, but cuts or mixtures. Of these, preference is given to those whose content of compounds having longer-chain radicals in the range from 16 to 18 carbon atoms is more than 20% by weight.
  • soaps suitable being saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids.
  • those soap mixtures are preferred which are composed of 50% to 100% by weight of saturated C 12 -C 18 fatty acid soaps and up to 50% by weight of oleic acid soap.
  • soap is included in amounts of from 0.1% to 10%, and more preferably from 0.5% to 5%, by weight.
  • enzymes present in agents of the invention are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase and mixtures thereof.
  • proteases derived from microorganisms, such as bacteria or fungi come into question.
  • the lipase which can be used can be prepared from Humicola lanuginosa, as described, for example, in European patent applications EP 258 068, EP 305 216 and EP 341 947, from Bacillus species, as described, for example, in international patent application WO 91/16422 or European patent application EP 384 717 , from Pseudomonas species, as for example in the European patent applications EP 468 102, EP 385 401, EP 375 102, EP 334 462, EP 331 376, EP 330 641, EP 214 761, EP 218 272 or EP 204 284 or the international Patent application WO 90/10695, from Fusarium species, as described for example in the European patent application EP 130,064, from Rhizopus species, as described for example in the European patent application EP 117 553, or from Aspergillus species, such as in the European Patent application EP 167 309 described, are obtained.
  • Suitable lipases are commercially available, for example, under the names Lipolase®, Lipozym®, Lipomax®, Arnano®-Lipase, Toyo-Jozo®-Lipase, Meito®-Lipase and Diosynth®-Lipase.
  • Suitable amylases are commercially available, for example, under the names Maxamyl®, Termamyl®, Duramyl® and Purafect® OxAm.
  • the usable cellulase may be a recoverable from bacteria or fungi enzyme, which has a pH optimum, preferably in the weakly acidic to slightly alkaline range of 6 to 9.5.
  • Such cellulases are known, for example, from German Offenlegungsschriften DE 31 17 250, DE 32 07 825, DE 32 07 847, DE 33 22 950 or European patent applications EP 265 832, EP 269 977, EP 270 974, EP 273 125 and EP 339 550 and international patent applications WO 95/02675 and WO 97/14804 and commercially available under the names Celluzyme®, Carezyme® and Ecostone®.
  • the sodium percarbonate particles PC1, PC2 and PC3 prepared according to Example 1 were each mixed in an amount of 13% by weight into an otherwise customary particulate detergent which additionally contained 15% by weight of surfactant, 0.75% by weight of enzyme mixture (protease / Amylase / cellulase) and 3.5% by weight of tetraacetyethylenediamine and, as builder block, 20.5% by weight of sodium carbonate, 5% by weight of sodium bicarbonate, 1% by weight of citric acid, 0.74% by weight of hydroxyethane-1 , 1-diphosphonic acid tetrasodium salt and 3% by weight of sodium polyacrylate.
  • enzyme mixture prote / Amylase / cellulase
  • tetraacetyethylenediamine tetraacetyethylenediamine
  • agents were also prepared which were otherwise equal but which contained the sodium percarbonate grades Q 30 and Q 35, respectively, which were used as starting material in Example 1 and coated only with sodium sulfate. Furthermore, for comparison, agents were prepared which contained 13% by weight of PC1, PC2 or PC3 and also corresponded in their other composition to the abovementioned agents, but whose builder block contained zeolite Na-A instead of sodium carbonate and sodium bicarbonate.
  • white test cloths contaminated with standardized test soils (A: blood / milk / ink, B: blood / milk / carbon black, C: milk cocoa) were at 40 ° C.

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  • Detergent Compositions (AREA)

Claims (17)

  1. Agent de lavage ou de nettoyage contenant des agents de blanchiment et des builders, sous forme de particules, contenant (A) un bloc de builder hydrosoluble exempt de phosphates, et (B) des particules de percarbonate de métal alcalin, lesquelles présentent une couche d'enrobage qui contient un silicate de métal alcalin, les agents ne contenant pas d'autres substances builders en tant que tels, qui soient hydrosolubles et exempts de phosphates, à l'exception des quantités qui peuvent être contenues d'une façon courante dans le commerce en de faibles quantités dans les autres ingrédients, en tant qu'impuretés ou additifs stabilisants.
  2. Agent selon la revendication 1, caractérisé en ce que la particule de percarbonate de métal alcalin présente au moins deux couches d'enrobage, une couche la plus intérieure contenant au moins un sel inorganique formant un hydrate et une couche extérieure contenant un silicate de métal alcalin.
  3. Agent selon la revendication 2, caractérisé en ce que la couche la plus intérieure constitue 2% en poids à 20% en poids de la particule enrobée.
  4. Agent selon la revendication 2 ou 3, caractérisé en ce que le sel inorganique formant un hydrate dans la couche la plus intérieure est choisi parmi les sulfates de métal alcalin, les carbonates de métal alcalin, les hydrogénocarbonates de métal alcalin, les borates de métal alcalin, les perborates de métal alcalin, et les mélanges de ceux-ci.
  5. Agent selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la couche contenant le silicate de métal alcalin représente 0,2% en poids à 3% en poids, en particulier 0,3% en poids jusqu'à moins de 1 % en poids de la particule enrobée.
  6. Agent selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le silicate de métal alcalin dans la couche d'enrobage présente un module (rapport molaire de SiO2 à l'oxyde de dimétal alcalin) supérieur à 2,5, en particulier dans la plage de 3 à 5.
  7. Agent selon l'une quelconque des revendications 1 à 6, caractérisé en ce que la proportion des particules de percarbonate de métal alcalin est de 6% en poids à 30% en poids, en particulier de 10% en poids à 25% en poids.
  8. Agent selon l'une quelconque des revendications 1 à 7, caractérisé en ce que la proportion du bloc de builder est au moins de 15% en poids.
  9. Agent selon l'une quelconque des revendications 1 à 8, caractérisé en ce que la proportion du bloc de builder s'élève jusqu'à 55% en poids, en particulier de 25% en poids à 50% en poids.
  10. Agent selon l'une quelconque des revendications 1 à 9, caractérisé en ce que le bloc de builder hydrosoluble (A) se compose des composants :
    a) 5% en poids à 35% en poids d'acide citrique, de citrate de métal alcalin et/ou de carbonate de métal alcalin, lequel peut être remplacé au moins partiellement par un hydrogénocarbonate de métal alcalin,
    b) jusqu'à 10% en poids de silicate de métal alcalin avec un module dans la plage de 1,8 à 2,5,
    c) jusqu'à 2% en poids d'acide phosphonique et/ou de phosphonate de métal alcalin, et
    d) jusqu'à 10% en poids d'un polycarboxylate polymère.
  11. Agent selon la revendication 10, caractérisé en ce que le bloc de builder contient au moins deux des composants b), c) et d) en des quantités supérieures à 0% en poids.
  12. Agent selon la revendication 10 ou 11, caractérisé en ce que 15% en poids à 25% en poids de carbonate de métal alcalin qui peut être remplacé au moins partiellement par de l'hydrogénocarbonate de métal alcalin, et jusqu'à 5% en poids, en particulier 0,5% en poids à 2,5% en poids d'acide citrique et/ou de citrate de métal alcalin sont contenus en tant que composant a).
  13. Agent selon la revendication 10 ou 11, caractérisé en ce que 5% en poids à 25% en poids, en particulier 5% en poids à 15% en poids d'acide citrique et/ou de citrate de métal alcalin, et jusqu'à 5% en poids, en particulier 1% en poids à 5% en poids de carbonate de métal alcalin, lequel peut être remplacé au moins partiellement par de l'hydrogénocarbonate de métal alcalin, sont contenus en tant que composant a).
  14. Agent selon l'une quelconque des revendications 10 à 13, caractérisé en ce que le composant a) présente du carbonate de métal alcalin et de l'hydrogénocarbonate de métal alcalin dans le rapport pondéral de 10:1 à 1:1.
  15. Agent selon l'une quelconque des revendications 10 à 14, caractérisé en ce que 1% en poids à 5% en poids de silicate de métal alcalin ayant un module dans la plage de 1,8 à 2,5 est contenu en tant que composant b).
  16. Agent selon l'une quelconque des revendications 10 à 15, caractérisé en ce que 0,05% en poids à 1% en poids d'acide phosphonique et/ou de phosphonate de métal alcalin, en particulier choisi parmi l'acide hydroxy- et/ou aminoalkylphosphonique et/ou leurs sels de métal alcalin, sont contenus en tant que composant c).
  17. Agent selon l'une quelconque des revendications 10 à 16, caractérisé en ce que 1,5% en poids à 5% en poids de polycarboxylate polymère, en particulier choisi parmi les produits de polymérisation ou de copolymérisation de l'acide acrylique, de l'acide méthacrylique et/ou de l'acide maléique, sont contenus en tant que composant d).
EP03767718A 2002-12-20 2003-12-02 Produits de lavage et de nettoyage contenant un agent de blanchiment Revoked EP1572851B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE10261161 2002-12-20
DE10261161 2002-12-20
DE10320196A DE10320196A1 (de) 2002-12-20 2003-05-07 Bleichmittelhaltige Wasch- oder Reinigungsmittel
DE10320196 2003-05-07
PCT/EP2003/013539 WO2004058931A1 (fr) 2002-12-20 2003-12-02 Produits de lavage et de nettoyage contenant un agent de blanchiment

Publications (2)

Publication Number Publication Date
EP1572851A1 EP1572851A1 (fr) 2005-09-14
EP1572851B1 true EP1572851B1 (fr) 2007-03-21

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EP03767718A Revoked EP1572851B1 (fr) 2002-12-20 2003-12-02 Produits de lavage et de nettoyage contenant un agent de blanchiment

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US (1) US7456143B2 (fr)
EP (1) EP1572851B1 (fr)
AT (1) ATE357497T1 (fr)
AU (1) AU2003292165A1 (fr)
DE (1) DE50306874D1 (fr)
ES (1) ES2283831T3 (fr)
WO (1) WO2004058931A1 (fr)

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ATE357497T1 (de) 2007-04-15
WO2004058931A1 (fr) 2004-07-15
US20050239681A1 (en) 2005-10-27
US7456143B2 (en) 2008-11-25
DE50306874D1 (de) 2007-05-03
ES2283831T3 (es) 2007-11-01
EP1572851A1 (fr) 2005-09-14
AU2003292165A1 (en) 2004-07-22

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