EP0559679A1 - Stabilisation of percarbonate - Google Patents

Stabilisation of percarbonate

Info

Publication number
EP0559679A1
EP0559679A1 EP19910920118 EP91920118A EP0559679A1 EP 0559679 A1 EP0559679 A1 EP 0559679A1 EP 19910920118 EP19910920118 EP 19910920118 EP 91920118 A EP91920118 A EP 91920118A EP 0559679 A1 EP0559679 A1 EP 0559679A1
Authority
EP
European Patent Office
Prior art keywords
percarbonate
acetic acid
compounds
hydrolysis conditions
acetylated
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.)
Withdrawn
Application number
EP19910920118
Other languages
German (de)
French (fr)
Inventor
Heinz-Manfred Wilsberg
Rolf Puchta
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 EP0559679A1 publication Critical patent/EP0559679A1/en
Withdrawn legal-status Critical Current

Links

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
    • C11D3/3937—Stabilising agents
    • C11D3/394—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
    • C01B15/055—Peroxyhydrates; Peroxyacids or salts thereof
    • C01B15/10—Peroxyhydrates; Peroxyacids or salts thereof containing carbon
    • C01B15/106—Stabilisation of the solid compounds, subsequent to the preparation or to the crystallisation, by additives or by coating

Definitions

  • the invention relates to the use of compounds which split off acetic acid under hydrolysis conditions to stabilize percarbonates and to the use of such compounds as stabilizers for percarbonates in bleaching, washing or cleaning agents.
  • Detergents and cleaning agents which contain a combination of an inorganic peroxide or perhydrate as a bleaching system and a bleach activator which forms an organic peracid under washing conditions have been known for a long time.
  • the most frequently used bleaching components containing active oxygen are the alkali perborates, percarbonates, persulfates and persilicates, among which sodium perborate, which is used as tetra- or monohydrate, occupies a dominant position.
  • Peroxo compounds stabilized by a coating of crystallized sodium carbonate in combination with other mineral salts are known from the German patent application DT 2417572.
  • the stabilizing effect of phosphate coatings is known from European patent application EP 24201.
  • German patent DE 25 31 466 proposes the use of certain rare earth complexes as stabilizers for percarbonates.
  • the stabilizing effect is due to the German patent specification DE 2655971 and the European patent specification EP 30 759 the coating of per compounds with fatty acids is known.
  • Bleaching agents which contain certain ⁇ -hydroxyacrylate polymers as stabilizers for per compounds are known from German laid-open specification DE 3337719 and European patent specification EP 021498.
  • the invention relates to the use of compounds which split off acetic acid under hydrolysis conditions for the stabilization of powdery percarbonate, in particular the use of the compounds which split off acetic acid under hydrolysis conditions as stabilizers for powdered percarbonate in solid bleaching, washing, cleaning and disinfecting agents.
  • the compounds which split off acetic acid under hydrolysis conditions are preferably selected from the group of the N- or O-acyl compounds and their mixtures. These include, in particular, multiply acetylated alkylamines, acetylated glycolurils, N-acetylated hydantoins, hydrazides, triazines, triazoles, urazoles, diketopiperazines, sulfurylamides, cyanurates and acetylated sugar derivatives.
  • N, N, N ', N'-tetraacetylethylenediamine, 1,5-diacetyl-2,4-dioxo-hexahydro-1,5,5-triazine, tetraacetylglycoluril, pentaacetylglucose and mixtures thereof is particularly preferred.
  • This group of compounds are well known cold bleach activators for peroxo compounds. These compounds had previously been assumed to have a precisely destabilizing effect in the presence of customary peroxo compounds and when water was ingress. It is all the more surprising to find that these substances known as activators are actually in combination with percarbo- act as stabilizers.
  • the stabilizing compounds can be in the form of powders, but also in the form of granules.
  • Such granules preferably consist of at least 90% by weight, in particular over 92% by weight, of the compound which splits off acetic acid under hydrolysis conditions, the remainder consisting of 100% by weight of granulation auxiliaries and water and inorganic salts.
  • TAED tetraacetylethylenediamine
  • the percarbonate stabilizers are preferably used in amounts such that the molar ratio of stabilizer to percarbonate is 1:50 to 1: 2, in particular 1:10 to 1: 2. Since these compounds act as bleach activators, that is to say react in the presence of water with peroxo compounds to form peracetic acid and thus give rise to a highly effective oxidizing agent in aqueous washing or cleaning solutions, it is all the more surprising that such substances in the Are able to stabilize percarbonate very effectively.
  • the percarbonate to be stabilized is preferably an alkali percarbonate, in particular sodium percarbonate.
  • Such percarbonates can be prepared by known processes, for example by adding aqueous hydrogen peroxide to the corresponding carbonate in accordance with German laid-open documents DE 2805338 or DE 2925 732, or by crystallization from an aqueous solution containing hydrogen peroxide in accordance with the German designations DE 2303627 or DE 2364634 ⁇ and optionally granulated with the aid of conventional granulation aids.
  • the percarbonate is preferably used in the form of powders with average particle sizes of 0.1 mm to 0.8 mm and bulk densities of 750 g / 1 to 1100 g / 1, in particular 850 g / 1 to 1000 g / 1.
  • powdery percarbonate can be stabilized very effectively.
  • a particular advantage of the invention is that the stabilizing effect of the compounds to be used according to the invention also comes into play when the percarbonate is part of a bleaching, washing or cleaning agent is present.
  • agents of this type can have all the constituents usually contained in them, which include, in particular, surfactants, builder substances, inorganic filler salts, enzymes, complexing agents for heavy metals, perfumes and dyes.
  • the bleaching, washing, cleaning or disinfecting agents preferably contain 5% by weight to 90% by weight, in particular 15% by weight to 80% by weight, of percarbonate stabilized according to the invention, the molar ratio of stabilizer to percarbonate being preferred 1:50 to 1: 2, in particular 1:10 to 1: 2.
  • the builder substances suitable for these agents are water-soluble or water-insoluble compounds or mixtures of two or more such compounds.
  • Suitable builder substances are, in particular, those from the class of the polycarboxylic acids, in particular polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, sheet silicates, in particular bentonites, aluminum silicates, in particular zeolites, alkali metal silicates, in particular sodium silicate and alkali metal carbonates, in particular sodium carbonate.
  • the aforementioned polycarboxylic acids are usually used in the form of their alkali metal salts, in particular their sodium or potassium salts.
  • the preferably incorporated zeolites are in particular those of the NaA or NaX type or mixtures thereof.
  • Such builder substances are preferably present in amounts from 20% by weight to 90% by weight, in particular from 40% by weight to 80% by weight.
  • the detergent is preferably present in the compositions in amounts of from 2% by weight to 40% by weight, in particular from 5% by weight to 20% by weight.
  • These are preferably anionic or nonionic surfactants or mixtures thereof.
  • Suitable anionic surfactants are in particular those of the sulfate or sulfonate type, but other types such as soaps, long-chain N-acyl sarcosinates, salts of fatty acid cyanamides or salts of ether carboxylic acids, such as are obtainable from long-chain alkyl polyglycol ethers and chloroacetic acid, can also be used.
  • the anionic surfactants are preferably used in the form of the alkali or ammonium salts, in particular the natural salts.
  • Particularly suitable surfactants of the sulfate type are the sulfuric acid monoesters of long-chain primary alcohols, natural and of synthetic origin with 10 to 20 carbon atoms and those of secondary alcohols of this chain length.
  • the sulfuric acid monoesters of the aliphatic primary or secondary alcohols ethoxylated with 1 to 6 moles of ethylene oxide come into consideration.
  • the sulfonate-type surfactants are primarily the alkylbenzenesulfonates with Cg to Cis alkyl groups and the esters of oc-sulfofatty acids.
  • alkanesulfonates which are obtainable from C12- to Ci8-alkanes or from corresponding olefins, and also the olefinsulfonates, as are obtained, for example, from long-chain monoolefins with an end or internal double bond by sulfonation with gaseous sulfur receives trioxide.
  • the nonionic surfactants in question include alkyl polyglycosides with 10 to 22 carbon atoms in the alkyl part and the alkoxylates, in particular the ethoxylates and / or propoxylates of linear or branched chain alcohols with 10 to 22 carbon 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.
  • corresponding ethoxylation and / or propoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the alcohols mentioned with regard to the alkyl part, and also from Alkylphenols with 5 to 12 carbon atoms in the alkyl radical can be used.
  • Alkylbenzenesulfonates with linear Cg to C15 alkyl groups, fatty alcohol sulfates with 12 to 18 carbon atoms and mixtures of these surfactants are preferably used.
  • the detergent, cleaning agent or disinfectant cannot contain inorganic filler salt, preferably in amounts of not more than 50% by weight, in particular 1% by weight to 30% by weight, of heavy metal complexing agent, preferably in amounts 10% by weight, in particular from 0.1% by weight to 2% by weight, and further additives customary in disinfectants, cleaning agents, bleaching agents and washing agents, such as microbicides, enzymes, dyes and / or fragrances .
  • Such constituents are each preferably present in amounts not exceeding 1% by weight, in particular from 0.05 to 0.5% by weight, based on the total composition.
  • the production of the means does not require any major technical effort. It can be done in a simple manner by mixing the powdered components. Simple mixing devices, such as paddle or drum mixers, are usually suitable for this. Even the use of automatically working Belt scales in combination with free-fall mixers are possible.
  • the components can be used as individual components or in the form of premixes.
  • the agents containing percarbonate stabilized according to the invention showed more than 60% or almost 90% (M7, M8, M9) of the activity of the sodium percarbonate used in each case, while the agents free of stabilizers only showed 10% to contained a maximum of 50% (V4, V5) of the sodium percarbonate used. Became even clearer the stabilizer effect at a storage temperature of 40 ° C under otherwise identical conditions; then the agents stabilized according to the invention contained more than 50% to more than 80% (M7), the comparative agents less than 10% to at most 30% of the percarbonate used.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Detergent Compositions (AREA)

Abstract

Par l'utilisation de composés séparant l'acide acétique dans des conditions d'hydrolyse, de préférence d'un groupe des substances N- ou O-acétylés, il est possible de stabiliser du percarbonate pulvérulent, en particulier dans des agents de blanchiment, de nettoyage et de désinfection, très efficacement contre la perte d'oxygène actif.By the use of compounds separating acetic acid under hydrolysis conditions, preferably from a group of N- or O-acetylated substances, it is possible to stabilize pulverulent percarbonate, in particular in bleaching agents, cleaning and disinfection, very effectively against loss of active oxygen.

Description

"Stabilisierung von Percarbonat" "Stabilization of percarbonate"
Die Erfindung betrifft die Verwendung von unter Hydrolysebedingungen Es¬ sigsäure abspaltenden Verbindungen zur Stabilisierung von Percarbonaten sowie die Verwendung derartiger Verbindungen als Stabilisatoren für Per- carbonate in Bleich-, Wasch- oder Reinigungsmitteln.The invention relates to the use of compounds which split off acetic acid under hydrolysis conditions to stabilize percarbonates and to the use of such compounds as stabilizers for percarbonates in bleaching, washing or cleaning agents.
Wasch- und Reinigungsmittel, die als Bleichsystem eine Kombination eines anorganischen Peroxids oder Perhydrats mit einem Bleichaktivator, der un¬ ter Waschbedingungen eine organische Persäure bildet, enthalten, sind seit langer Zeit bekannt. Die am häufigsten eingesetzten aktivsauerstoffhal- tigen Bleichkomponenten sind die Alkaliperborate, -percarbonate, -persul- fate und -persilikate, unter denen Natriumperborat, das als Tetra- oder Monohydrat verwendet wird, eine dominierende Position einnimmt. Da die Freisetzung von Aktivsauerstoff aus der Perverbindung, die erst unter den wäßrigen Waschbedingungen erfolgen soll, auch bei der Herstellung und insbesondere der Lagerung derartiger Mittel ablaufen kann, wodurch die Verfügbarkeit der Perverbindung für den eigentlichen Anwendungszweck zu¬ rückgeht, wird seit langer Zeit nach Stabilisatoren für die erwähnten Bleichsysteme gesucht. So ist aus der deutschen Offenlegungsschrift DT 22 14500 die stabilisierende Wirkung der Ethylendia intetramethylen- phosphonsäure bekannt. Die Umhüllung des Oxidationsmittels mit Polyvinyl¬ chlorid enthaltenden Mischpolymerisaten ist in den deutschen Offenle- gungsschriften DT 2402 392 und DT 2402393 vorgeschlagen worden. Durch eine Umhüllung aus kristallisiertem Natriumcarbonat in Kombination mit anderen Mineralsalzen stabilisierte Peroxoverbindungen sind aus der deutschen Offenlegungsschrift DT 2417572 bekannt. Bekannt ist aus der europäischen Patentanmeldung EP 24201 die stabilisierende Wirkung von Phosphat-Umhüllungen. In der deutschen Patentschrift DE 25 31 466 wird die Verwendung bestimmter Seltenerd-Komplexe als Stabilisatoren für Percar¬ bonate vorgeschlagen. Aus der deutschen Patentschrift DE 2655971 und der europäischen Patentschrift EP 30 759 ist die stabilisierende Wirkung durch die Umhüllung von Perverbindungen mit Fettsäuren bekannt. Bleichmittel, die bestimmte α-Hydroxyacrylat-Polymerisate als Stabilisatoren für Per¬ verbindungen enthalten, sind aus der deutschen Offenlegungsschrift DE 3337719 und der europäischen Patentschrift EP 021498 bekannt.Detergents and cleaning agents which contain a combination of an inorganic peroxide or perhydrate as a bleaching system and a bleach activator which forms an organic peracid under washing conditions have been known for a long time. The most frequently used bleaching components containing active oxygen are the alkali perborates, percarbonates, persulfates and persilicates, among which sodium perborate, which is used as tetra- or monohydrate, occupies a dominant position. Since the release of active oxygen from the per-compound, which is only to take place under the aqueous washing conditions, can also take place during the production and in particular the storage of such agents, as a result of which the availability of the per-compound for the actual intended use decreases, stabilizers have long been used searched for the bleaching systems mentioned. The stabilizing effect of ethylenedia intetramethylene-phosphonic acid is known from German Offenlegungsschrift DT 22 14500. The coating of the oxidizing agent with copolymers containing polyvinyl chloride has been proposed in German Offenlegungsschriften DT 2402 392 and DT 2402393. Peroxo compounds stabilized by a coating of crystallized sodium carbonate in combination with other mineral salts are known from the German patent application DT 2417572. The stabilizing effect of phosphate coatings is known from European patent application EP 24201. German patent DE 25 31 466 proposes the use of certain rare earth complexes as stabilizers for percarbonates. The stabilizing effect is due to the German patent specification DE 2655971 and the European patent specification EP 30 759 the coating of per compounds with fatty acids is known. Bleaching agents which contain certain α-hydroxyacrylate polymers as stabilizers for per compounds are known from German laid-open specification DE 3337719 and European patent specification EP 021498.
Aus der Vielzahl der vorgeschlagenen Stabilisierungsmöglichkeiten wird die Schwierigkeit deutlich, peroxidische Bleichkomponenten stabil in Wasch¬ oder Reinigungsmittel einzuarbeiten. Für Percarbonat-haltige Bleichsysteme ist das Problem der mangelhaften Lagerstab lität besonders schwer zu lö¬ sen, da dieses Perhydrat extrem hydrolyseanfällig ist und sowohl von der normalen Luftfeuchtigkeit rasch zersetzt wird als auch in Wasser enthal¬ tenden Bleichmitteln, die in wasserundurchlässigen Verpackungen gelagert werden, unter Verlust von Aktivsauerstoff zerfällt.The difficulty of incorporating peroxidic bleaching components stably into detergents or cleaning agents is evident from the large number of proposed stabilization options. For percarbonate-containing bleaching systems, the problem of inadequate storage stability is particularly difficult to solve, since this perhydrate is extremely susceptible to hydrolysis and is rapidly decomposed by normal atmospheric humidity, as well as in bleaches containing water, which are stored in water-impermeable packaging. decays with loss of active oxygen.
Überraschenderweise wurde nun ein neuer Weg gefunden, um Percarbonat zu stabilisieren.Surprisingly, a new way has now been found to stabilize percarbonate.
Gegenstand der Erfindung ist die Verwendung von unter Hydrolysebedingungen Essigsäure abspaltenden Verbindungen zur Stabilisierung von pulverförmigem Percarbonat, insbesondere die Verwendung der unter Hydrolysebedingungen Essigsäure abspaltenden Verbindungen als Stabilisatoren für pulverförmiges Percarbonat in festen Bleich-, Wasch-, Reinigungs- und Desinfektionsmit¬ teln.The invention relates to the use of compounds which split off acetic acid under hydrolysis conditions for the stabilization of powdery percarbonate, in particular the use of the compounds which split off acetic acid under hydrolysis conditions as stabilizers for powdered percarbonate in solid bleaching, washing, cleaning and disinfecting agents.
Die unter Hydrolysebedingungen Essigsäure abspaltenden Verbindungen werden vorzugsweise aus der Gruppe der N- oder O-AcylVerbindungen und deren Ge¬ mischen ausgewählt. Zu diesen gehören insbesondere mehrfach acetylierte Alkyleπdiamine, acetylierte Glykolurile, N-acetylierte Hydantoine, Hydrazide, Triazine, Triazole, Urazole, Diketopiperazine, Sulfurylamide, Cyanurate und acetylierte Zuckerderivate. Besonders bevorzugt ist die Verwendung von N,N,N' ,N'-Tetraacetylethylendiamin, l,5-Diacetyl-2,4-dioxo- hexahydro-l,3,5-triazin, Tetraacetylglykoluril, Pentaacetylglucose und deren Gemischen. Bei dieser Gruppe von Verbindungen handelt es sich um wohlbekannte Kaltbleichaktivatoren für Peroxoverbindungen. Von diesen Verbindungen war bisher angenommmen worden, daß sie in Gegenwart von üblichen Peroxoverbindungen und bei Zutritt von Wasser gerade destabili¬ sierend wirken. Um so überraschender ist die Festsstellung, daß diese als Aktivatoren bekannten Substanzen tatsächlich in Kombination mit Percarbo- nat als Stabilisatoren wirken. Die stabilisierend wirkenden Verbindungen können in Form von Pulvern, aber auch als Granulate vorliegen. Derartige Granulate bestehen dabei vorzugsweise zu mindestens 90 Gew.-%, insbesonde¬ re über 92 Gew.-% aus der unter Hydrolysebedingungen Essigsäure abspalten¬ den Verbindung, wobei der Rest auf 100 Gew.-% aus Granulationshilfsmitteln und Wasser sowie anorganischen Salzen besteht. Unter den granulierten Sta¬ bilisatoren ist mit Hilfe von Carboxymethylcellulose granuliertes Tetra- acetylethylendiamin (TAED) mit mittleren Korngrößen von 0,01 mm bis 0,8 mm, wie es beispielsweise nach dem in der europäischen Patentschrift EP 037026 beschriebenen Verfahren hergestellt werden kann, besonders bevorzugt.The compounds which split off acetic acid under hydrolysis conditions are preferably selected from the group of the N- or O-acyl compounds and their mixtures. These include, in particular, multiply acetylated alkylamines, acetylated glycolurils, N-acetylated hydantoins, hydrazides, triazines, triazoles, urazoles, diketopiperazines, sulfurylamides, cyanurates and acetylated sugar derivatives. The use of N, N, N ', N'-tetraacetylethylenediamine, 1,5-diacetyl-2,4-dioxo-hexahydro-1,5,5-triazine, tetraacetylglycoluril, pentaacetylglucose and mixtures thereof is particularly preferred. This group of compounds are well known cold bleach activators for peroxo compounds. These compounds had previously been assumed to have a precisely destabilizing effect in the presence of customary peroxo compounds and when water was ingress. It is all the more surprising to find that these substances known as activators are actually in combination with percarbo- act as stabilizers. The stabilizing compounds can be in the form of powders, but also in the form of granules. Such granules preferably consist of at least 90% by weight, in particular over 92% by weight, of the compound which splits off acetic acid under hydrolysis conditions, the remainder consisting of 100% by weight of granulation auxiliaries and water and inorganic salts. Among the granulated stabilizers, tetraacetylethylenediamine (TAED) with average grain sizes of 0.01 mm to 0.8 mm, such as can be produced, for example, by the process described in European Patent EP 037026, is special with the aid of carboxymethyl cellulose prefers.
Die Percarbonat-Stabilisatoren werden vorzugsweise in solchen Mengen ver¬ wendet, daß das Molverhältnis von Stabilisator zu Percarbonat 1:50 bis 1:2, insbesondere 1:10 bis 1:2 beträgt. Da diese Verbindungen als Bleich¬ aktivatoren wirken, das heißt in Gegenwart von Wasser mit Peroxoverbin¬ dungen unter Bildung von Peressigsäure reagieren und damit in wäßrigen Wasch- oder Reinigungslösungen ein hochwirksames Oxidationsmittel entste¬ hen lassen, muß umso mehr überraschen, daß derartige Substanzen in der Lage sind, Percarbonat sehr wirksam zu stabilisieren.The percarbonate stabilizers are preferably used in amounts such that the molar ratio of stabilizer to percarbonate is 1:50 to 1: 2, in particular 1:10 to 1: 2. Since these compounds act as bleach activators, that is to say react in the presence of water with peroxo compounds to form peracetic acid and thus give rise to a highly effective oxidizing agent in aqueous washing or cleaning solutions, it is all the more surprising that such substances in the Are able to stabilize percarbonate very effectively.
Bei dem zu stabilisierenden Percarbonat handelt es sich vorzugsweise um ein Alkalipercarbonat, insbesondere um Natriumpercarbonat. Derartige Per- carbonate können nach bekannten Verfahren, beispielsweise durch Zugabe von wäßrigem Wasserstoffperoxid zu dem entsprechenden Carbonat gemäß den deutschen Offenlegungsschriften DE 2805338 oder DE 2925 732 oder durch Kristallisation aus einer wäßrigen, Wasserstoffperoxidhaltigen Lösung ge¬ mäß den deutschen Auslegeschriften DE 2303627 oder DE 2364634 herge¬ stellt und gegebenenfalls mit Hilfe üblicher Granulationshilfsmittel gra¬ nuliert werden. Vorzugsweise wird das Percarbonat in Form von Pulvern mit mittleren Teilchengrößen von 0,1 mm bis 0,8 mm und Schüttgewichten von 750 g/1 bis 1100 g/1, insbesondere 850 g/1 bis 1000 g/1 eingesetzt.The percarbonate to be stabilized is preferably an alkali percarbonate, in particular sodium percarbonate. Such percarbonates can be prepared by known processes, for example by adding aqueous hydrogen peroxide to the corresponding carbonate in accordance with German laid-open documents DE 2805338 or DE 2925 732, or by crystallization from an aqueous solution containing hydrogen peroxide in accordance with the German designations DE 2303627 or DE 2364634 ¬ and optionally granulated with the aid of conventional granulation aids. The percarbonate is preferably used in the form of powders with average particle sizes of 0.1 mm to 0.8 mm and bulk densities of 750 g / 1 to 1100 g / 1, in particular 850 g / 1 to 1000 g / 1.
Durch die erfindungsgemäße Verwendung kann pulverförmiges Percarbonat als solches sehr wirksam stabilisiert werden. Als besonderer Vorteil der Er¬ findung ist jedoch zu werten, daß die Stabilisierungswirkung der erfin¬ dungsgemäß zu verwendenden Verbindungen auch zum Tragen kommt, wenn das Percarbonat als Bestandteil eines Bleich-, Wasch- oder Reinigungsmittels vorliegt. Dabei können derartige Mittel alle üblicherweise in diesen ent¬ haltenen Bestandteile aufweisen, zu denen insbesondere Tenside, Builder- substanzen, anorganische Füllsalze, Enzyme, Komplexbildner für Schwer¬ metalle, Parfüms und Farbstoffe gehören.As a result of the use according to the invention, powdery percarbonate can be stabilized very effectively. A particular advantage of the invention, however, is that the stabilizing effect of the compounds to be used according to the invention also comes into play when the percarbonate is part of a bleaching, washing or cleaning agent is present. In this case, agents of this type can have all the constituents usually contained in them, which include, in particular, surfactants, builder substances, inorganic filler salts, enzymes, complexing agents for heavy metals, perfumes and dyes.
Die Bleich-, Wasch-, Reinigungs- oder Desinfektionsmittel enthalten dabei vorzugsweise 5 Gew.-% bis 90 Gew.-%, insbesondere 15 Gew.-% bis 80 Gew.-% erfindungsgemäß stabilisiertes Percarbonat, wobei das Molverhältnis von Stabilisator zu Percarbonat vorzugsweise 1:50 bis 1:2, insbesondere 1:10 bis 1:2 beträgt.The bleaching, washing, cleaning or disinfecting agents preferably contain 5% by weight to 90% by weight, in particular 15% by weight to 80% by weight, of percarbonate stabilized according to the invention, the molar ratio of stabilizer to percarbonate being preferred 1:50 to 1: 2, in particular 1:10 to 1: 2.
Bei den für diese Mittel geeigneten Buildersubstanzen handelt es sich um wasserlösliche oder wasserunlösliche Verbindungen oder um Gemische aus zwei oder mehreren derartiger Verbindungen. Geeignete Buildersubstanzen sind insbesondere solche aus der Klasse der Polycarbonsäuren, insbesondere polymere Acrylsäuren, Methacrylsäuren, Maleinsäuren und Mischpolymere aus diesen, Schichtsilikate, insbesondere Bentonite, Alu osilikate, insbeson¬ dere Zeolithe, Alkalisilikate, insbesondere Natriumsilikat und Alkalicarbo- nate, insbesondere Natriumcarbonat. Die vorgenannten Polycarbonsäuren werden üblicherweise in Form ihrer Alkalisalze, insbesondere ihrer Natrium- oder Kaliumsalze eingesetzt. Die vorzugsweise eingearbeiteten Zeolithe sind insbesondere solche des NaA- oder NaX-Typs oder deren Ge¬ mische. Derartige Buildersubstanzen sind vorzugsweise in Mengen von 20 Gew.-% bis 90 Gew.-%, insbesondere von 40 Gew.-% bis 80 Gew.-% enthalten.The builder substances suitable for these agents are water-soluble or water-insoluble compounds or mixtures of two or more such compounds. Suitable builder substances are, in particular, those from the class of the polycarboxylic acids, in particular polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, sheet silicates, in particular bentonites, aluminum silicates, in particular zeolites, alkali metal silicates, in particular sodium silicate and alkali metal carbonates, in particular sodium carbonate. The aforementioned polycarboxylic acids are usually used in the form of their alkali metal salts, in particular their sodium or potassium salts. The preferably incorporated zeolites are in particular those of the NaA or NaX type or mixtures thereof. Such builder substances are preferably present in amounts from 20% by weight to 90% by weight, in particular from 40% by weight to 80% by weight.
Tensid ist in den Mitteln vorzugsweise in Mengen von 2 Gew.-% bis 40 Gew.-%, insbesondere von 5 Gew.-% bis 20 Gew.-%, enthalten. Vorzugsweise handelt es sich dabei um anioπische oder nichtionische Tenside oder um deren Ge¬ mische.The detergent is preferably present in the compositions in amounts of from 2% by weight to 40% by weight, in particular from 5% by weight to 20% by weight. These are preferably anionic or nonionic surfactants or mixtures thereof.
Geeignete anionische Tenside sind insbesondere solche vom Sulfat- oder Sulfonattyp, doch können auch andere Typen wie Seifen, langkettige N-Acyl- sarkosinate, Salze von Fettsäurecyanamiden oder Salze von Ethercarbonsäu- ren, wie sie aus langkettigen Alkylpolyglykolethern und Chloressigsäure zugänglich sind, verwendet werden. Die anionischen Tenside werden vorzugsweise in Form der Alkali- oder Ammoniumsalze, insbesondere der Na- trfu salze verwendet. Besonders geeignete Tenside vom Sulfattyp sind die Schwefelsäuremonoester von langkettigen primären Alkoholen natürlichen und synthetischen Ursprungs mit 10 bis 20 C-Atomen und solche von sekundären Alkoholen dieser Kettenlängen. Daneben kommen die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten aliphatischen primären oder sekundären Alkohole in Betracht. Bei den Tensiden vom Sulfonattyp handelt es sich in erster Linie um die Alkylbenzolsulfonate mit Cg- bis Cis-Alkylgruppen und um die Ester von oc-Sulfofettsäuren. Weitere brauch¬ bare Tenside sind die Alkansulfonate, die aus C12- bis Ci8-Alkanen oder aus entsprechnenden Olefine erhältlich sind, sowie die Olefinsulfonate, wie man sie zum Beispiel aus langkettigen Monoolefinen mit end- oder in¬ nenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefel¬ trioxid erhält. Zu den in Frage kommenden nichtionischen Tensiden gehö¬ ren Alkylpolyglykoside mit 10 bis 22 C-Atomen im Alkylteil und die Alkoxy- late, insbesondere die Ethoxylate und/oder Propoxylate von linearen oder verzweigtkettigen Alkoholen mit 10 bis 22 C-Atomen, vorzugsweise 12 bis 18 C-Atomen. Der Alkoxylierungsgrad der Alkohole liegt dabei in der Regel zwischen 1 und 20, vorzugsweise zwischen 3 und 10. Außerdem sind entspre¬ chende Ethoxylierungs- und/oder Propoxylierungsprodukte von Alkylaminen, vicinalen Diolen und Carbonsäureamiden, die hinsichtlich des Alkylteils den genannten Alkoholen entsprechen, sowie von Alkylphenolen mit 5 bis 12 C-Atomen im Alkylrest verwendbar.Suitable anionic surfactants are in particular those of the sulfate or sulfonate type, but other types such as soaps, long-chain N-acyl sarcosinates, salts of fatty acid cyanamides or salts of ether carboxylic acids, such as are obtainable from long-chain alkyl polyglycol ethers and chloroacetic acid, can also be used. The anionic surfactants are preferably used in the form of the alkali or ammonium salts, in particular the natural salts. Particularly suitable surfactants of the sulfate type are the sulfuric acid monoesters of long-chain primary alcohols, natural and of synthetic origin with 10 to 20 carbon atoms and those of secondary alcohols of this chain length. In addition, the sulfuric acid monoesters of the aliphatic primary or secondary alcohols ethoxylated with 1 to 6 moles of ethylene oxide come into consideration. The sulfonate-type surfactants are primarily the alkylbenzenesulfonates with Cg to Cis alkyl groups and the esters of oc-sulfofatty acids. Other surfactants that can be used are the alkanesulfonates which are obtainable from C12- to Ci8-alkanes or from corresponding olefins, and also the olefinsulfonates, as are obtained, for example, from long-chain monoolefins with an end or internal double bond by sulfonation with gaseous sulfur receives trioxide. The nonionic surfactants in question include alkyl polyglycosides with 10 to 22 carbon atoms in the alkyl part and the alkoxylates, in particular the ethoxylates and / or propoxylates of linear or branched chain alcohols with 10 to 22 carbon 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. In addition, corresponding ethoxylation and / or propoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the alcohols mentioned with regard to the alkyl part, and also from Alkylphenols with 5 to 12 carbon atoms in the alkyl radical can be used.
Vorzugsweise werden Alkylbenzolsulfonate mit linearen Cg- bis Ci5~Alkyl- gruppen, Fettalkoholsulfate mit 12 bis 18 C-Atomen und Gemische dieser Tenside verwendet.Alkylbenzenesulfonates with linear Cg to C15 alkyl groups, fatty alcohol sulfates with 12 to 18 carbon atoms and mixtures of these surfactants are preferably used.
Zusätzlich kann das Wasch-, Reinigungs- oder Desinfektionsmittel anorga¬ nisches Füllsalz, vorzugsweise in Mengen nicht über 50 Gew.-%, insbeson¬ dere 1 Gew.-% bis 30 Gew.-%, Schwermetall-Komplexbildner, vorzugsweise in Mengen nicht über 10 Gew.-%, insbesondere von 0,1 Gew.-% bis 2 Gew.-%, und weitere in Desinfektions-, Reinigungs-, Bleich- und Waschmitteln übliche Zusatzstoffe, wie Mikrobizide, Enzyme, Farbstoffe und/oder Duftstoffe, enthalten. Derartige Bestandteile sind jeweils vorzugsweise in Mengen nicht über 1 Gew.-%, insbesondere von 0,05 bis 0,5 Gew.-%, bezogen auf das gesamte Mittel, enthalten.In addition, the detergent, cleaning agent or disinfectant cannot contain inorganic filler salt, preferably in amounts of not more than 50% by weight, in particular 1% by weight to 30% by weight, of heavy metal complexing agent, preferably in amounts 10% by weight, in particular from 0.1% by weight to 2% by weight, and further additives customary in disinfectants, cleaning agents, bleaching agents and washing agents, such as microbicides, enzymes, dyes and / or fragrances . Such constituents are each preferably present in amounts not exceeding 1% by weight, in particular from 0.05 to 0.5% by weight, based on the total composition.
Die Herstellung der Mittel erfordert keinen größeren technischen Aufwand. Sie kann in einfacher Weise durch Mischen der pulverförmigen Bestandteile erfolgen. Meist sind dafür einfache Mischapparaturen, wie Schaufel- oder Trommelmischer geeignet. Auch die Verwendung automatisch arbeitender Bandwaagen in Kombination mit Freifallmischern ist möglich. Dabei können die Bestandteile als Einzelkomponenten oder in Form von Vorgemischen ein¬ gesetzt werden.The production of the means does not require any major technical effort. It can be done in a simple manner by mixing the powdered components. Simple mixing devices, such as paddle or drum mixers, are usually suitable for this. Even the use of automatically working Belt scales in combination with free-fall mixers are possible. The components can be used as individual components or in the form of premixes.
BeispieleExamples
Beispiel 1example 1
Durch Versprühen von etwa 35 Gew.-% Wasser enthaltenden Aufschlämmungen, die auf 60 °C bis 70 °C erwärmt worden waren, unter einem Druck von etwa 60 bar und Temperaturen des Trocknungsgases von 220 °C bis 230 °C wurden die in Tabelle 1 durch ihre Zusammensetzung charakterisierten Pulver Pl bis P5 hergestellt. Diese wurden in einem Freifall ischer mit den in Ta¬ belle 2 angegebenen Mengen an Natriumpercarbonat und Stabilisator ver¬ mischt, so daß die Wasch- und Bleichmittel Ml bis M9 als freifließende, nicht klumpende Pulver mit Schüttdichten von etwa 560 bis 620 Gramm pro Liter entstanden. Ihre Bleichleistung unter Waschbedingungen war in allenBy spraying slurries containing about 35% by weight of water, which had been heated to 60 ° C to 70 ° C, under a pressure of about 60 bar and temperatures of the drying gas of 220 ° C to 230 ° C, the in Table 1 Powder P1 to P5 characterized by their composition. In a free fall, these were mixed with the amounts of sodium percarbonate and stabilizer indicated in Table 2, so that the detergents and bleaches M1 to M9 were formed as free-flowing, non-clumping powders with bulk densities of about 560 to 620 grams per liter . Their bleaching performance under washing conditions was in all
Tabelle 1: Zusammensetzun der Pulverkom onenten Gew.-Table 1: Composition of the powder components by weight
a) 3- bis 5-fach ethoxylierter (Hersteller Henkel) a ) 3 to 5 times ethoxylated (Manufacturer Henkel)
-) Tetra-Na-hydroxyethan-l,l-diphosphonat (Hersteller Henkel) c) Acrylsäure/Maleinsäure-Copolymer (30:70), Natriumsalz (Hersteller BASF) Fällen zumindest nicht schlechter als die von zu Vergleichszwecken herge¬ stellten Mitteln, die statt Natriumpercarbonat Natriumperborat enthielten. Zum Vergleich in Lagertests wurden auf die gleiche Weise die stabilisator¬ freien Mittel VI bis V5 hergestellt.-) Tetra-Na-hydroxyethane-l, l-diphosphonate (manufacturer Henkel) c ) acrylic acid / maleic acid copolymer (30:70), sodium salt (manufacturer BASF) Cases at least not worse than that of agents produced for comparison purposes, which contained sodium perborate instead of sodium percarbonate. For comparison in storage tests, the stabilizer-free agents VI to V5 were produced in the same way.
Tabelle 2: Zusammensetzung der Mittel [Gew.-%]Table 2: Composition of the agents [% by weight]
a) Natriumpercarbonat, Aktivsauerstoffgehalt 14 % (Hersteller Interox) b) N N'.N'-Tetraacetylethylendiamin-Granulat gemäß EP 037 026, 94-pro¬ zentig c) N,N,N' ,N'-Tetraacetylethylendiamin-Pulver a ) Sodium percarbonate, active oxygen content 14% (manufacturer Interox) b ) N N'.N'-tetraacetylethylenediamine granules according to EP 037 026, 94 percent c ) N, N, N ', N'-tetraacetylethylenediamine powder
-) l,5-Diacetyl-2,4-dioxo-hexahydro-l,3,5-triazin - Granulat, 77-prozentig (Hersteller Leuna Werke AG)- ) l, 5-diacetyl-2,4-dioxo-hexahydro-l, 3,5-triazine - granules, 77 percent (manufacturer Leuna Werke AG)
Nach Lagerungsdauern von 16 Wochen bei 30 °C in wasserundurchlässigen Kunststoffbehältern wiesen die erfindungsgemäß stabilisiertes Percarbonat enthaltenden Mittel über 60 % beziehungsweise fast 90 % (M7, M8, M9) der Aktivität des jeweils eingesetzten Natriumpercarbonats auf, während die stabilisatorfreien Mittel nur noch 10 % bis maximal 50 % (V4, V5) des jeweils eingesetzten Natriumpercarbonats enthielten. Noch deutlicher wurde die Stabilisatorwirkung bei einer Lagerungtemperatur von 40 °C unter an¬ sonsten gleichen Bedingungen; dann enthielten die erfindungsgemäß stabi¬ lisierten Mitttel über 50 % bis über 80 % (M7), die Vergleichsmittel unter 10 % bis höchstens 30 % des eingesetzten Percarbonats. After storage periods of 16 weeks at 30 ° C. in water-impermeable plastic containers, the agents containing percarbonate stabilized according to the invention showed more than 60% or almost 90% (M7, M8, M9) of the activity of the sodium percarbonate used in each case, while the agents free of stabilizers only showed 10% to contained a maximum of 50% (V4, V5) of the sodium percarbonate used. Became even clearer the stabilizer effect at a storage temperature of 40 ° C under otherwise identical conditions; then the agents stabilized according to the invention contained more than 50% to more than 80% (M7), the comparative agents less than 10% to at most 30% of the percarbonate used.

Claims

Patentansprüche Claims
1. Verwendung von unter Hydrolysebedingungen Essigsäure abspaltenden Verbindungen zur Stabilisierung von pulverförmigem Percarbonat.1. Use of compounds which split off acetic acid under hydrolysis conditions for the stabilization of powdered percarbonate.
2. Verwendung von unter Hydrolysebedingungen Essigsäure abspaltenden Verbindungen als Stabilisatoren für Percarbonat in Bleich-, Wasch-, Reinigungs- und Desinfektionsmitteln.2. Use of compounds which release acetic acid under hydrolysis conditions as stabilizers for percarbonate in bleaching, washing, cleaning and disinfecting agents.
3. Verwendung nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß die unter Hydrolysebedingungen Essigsäure abspaltenden Verbin¬ dungen aus der Gruppe der N- oder O-acetylierten Substanzen umfassend mehrfach acetylierte Alkylendiamine, acetylierte Glykolurile, N- acetylierte Hydantoine, Hydrazide, Triazine, Triazole, Urazole, Diketopiperazine, Sulfurylamide, Cyanurate und acetylierte Zuckerde¬ rivate sowie deren Gemische ausgewählt sind.3. Use according to one of claims 1 or 2, characterized in that the compounds which split off under hydrolysis conditions are acetic acid from the group of N- or O-acetylated substances, including multiply acetylated alkylenediamines, acetylated glycolurils, N-acetylated hydantoins, hydrazides, triazines , Triazoles, urazoles, diketopiperazines, sulfurylamides, cyanurates and acetylated sugar derivatives and mixtures thereof are selected.
4. Verwendung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die unter Hydrolysebedingungen Essigsäure abspaltenden Verbin¬ dungen aus der Gruppe umfassend N,N,N' ,N'-Tetraacetylethylendiamin, l,5-Diacetyl-2,4-dioxohexahydro-l,3,5-triazin, Tetraacetylglykoluril , Pentaacetylglukose und deren Gemische ausgewählt sind.4. Use according to one of claims 1 to 3, characterized in that the compounds which split off under hydrolysis conditions acetic acid from the group comprising N, N, N ', N'-tetraacetylethylenediamine, 1,5-diacetyl-2,4-dioxohexahydro -l, 3,5-triazine, tetraacetylglycoluril, pentaacetylglucose and mixtures thereof are selected.
5. Verwendung nach Anspruch 4, dadurch gekennzeichnet, daß die unter Hy¬ drolysebedingungen Essigsäure abspaltende Verbindung mit Hilfe von Carboxymethylcellulose granuliertes N,N,N' ,N'-Tetraacetylethylendiamin mit mittleren Korngrößen von 0,01 mm bis 0,8 mm ist.5. Use according to claim 4, characterized in that the compound which releases acetic acid under hydrolysis conditions is N, N, N ', N'-tetraacetylethylenediamine granulated with the aid of carboxymethyl cellulose and having average grain sizes of 0.01 mm to 0.8 mm.
6. Verwendung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß es sich bei dem zu stabilisierenden Percarbonat um ein Alkaliper- carbonat, insbesondere um Natriumpercarbonat handelt.6. Use according to one of claims 1 to 5, characterized in that the percarbonate to be stabilized is an alkali percarbonate, in particular sodium percarbonate.
7. Verwendung nach Anspruch 6, dadurch gekennzeichnet, daß das Alkali- percarbonat eine mittlere Teilchengrößen von 0,1 mm bis 0,8 mm und ein Schüttgewicht von 750 g/1 bis 1100 g/1, insbesondere 850 g/1 bis 1000 g/1 aufweist. 7. Use according to claim 6, characterized in that the alkali percarbonate has an average particle size of 0.1 mm to 0.8 mm and a bulk density of 750 g / 1 to 1100 g / 1, in particular 850 g / 1 to 1000 g / 1.
8. Verwendung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß das MolVerhältnis von unter Hydrolysebedingungen Essigsäure ab¬ spaltender Verbindung zu Percarbonat im Bereich von 1:50 bis 1:2, insbesondere von 1:10 bis 1:2 liegt. 8. Use according to one of claims 1 to 7, characterized in that the molar ratio of the compound which releases acetic acid under hydrolysis conditions to the percarbonate is in the range from 1:50 to 1: 2, in particular from 1:10 to 1: 2.
EP19910920118 1990-12-01 1991-11-22 Stabilisation of percarbonate Withdrawn EP0559679A1 (en)

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DE19904038391 DE4038391A1 (en) 1990-12-01 1990-12-01 STABILIZATION OF PERCARBONATE
DE4038391 1990-12-01

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EP0559679A1 true EP0559679A1 (en) 1993-09-15

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DE4424005A1 (en) * 1994-07-07 1996-01-11 Henkel Kgaa Powdery bleach and detergent

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AT368982B (en) * 1975-07-21 1982-11-25 Treibacher Chemische Werke Ag STABILIZERS FOR ALKALIPER CARBONATES
JP2860798B2 (en) * 1989-06-27 1999-02-24 東海電化工業株式会社 Safe sodium percarbonate composition
GB8925285D0 (en) * 1989-11-09 1989-12-28 Unilever Plc Bleaching composition

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