EP0200163B1 - Bleaching agent, its preparation and its use - Google Patents

Bleaching agent, its preparation and its use Download PDF

Info

Publication number
EP0200163B1
EP0200163B1 EP86105669A EP86105669A EP0200163B1 EP 0200163 B1 EP0200163 B1 EP 0200163B1 EP 86105669 A EP86105669 A EP 86105669A EP 86105669 A EP86105669 A EP 86105669A EP 0200163 B1 EP0200163 B1 EP 0200163B1
Authority
EP
European Patent Office
Prior art keywords
weight
acid
bleaching agent
granules
granulate
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.)
Expired
Application number
EP86105669A
Other languages
German (de)
French (fr)
Other versions
EP0200163A3 (en
EP0200163A2 (en
Inventor
Jochen Dr. Jacobs
Edgar Dr. Köppelmann
Martin Dr. Witthaus
Manfred Dr. Dankowski
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6269591&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0200163(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT86105669T priority Critical patent/ATE46916T1/en
Publication of EP0200163A2 publication Critical patent/EP0200163A2/en
Publication of EP0200163A3 publication Critical patent/EP0200163A3/en
Application granted granted Critical
Publication of EP0200163B1 publication Critical patent/EP0200163B1/en
Expired 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
    • C11D3/3945—Organic per-compounds

Definitions

  • the present invention relates to bleaching agents in granular form which contain solid aliphatic peroxycarboxylic acid as the bleaching component.
  • Bleaching agents based on peroxygen compounds are widely used in the field of textile bleaching.
  • hydrogen peroxide and its inorganic derivatives such as sodium perborate and sodium percarbonate
  • mild oxidizing agents and on the other hand have a good bleaching capacity at sufficiently high temperatures.
  • stronger oxidizing agents such as peroxycarboxylic acids
  • peroxycarboxylic acids also called percarboxylic acids or simply peracids, are very aggressive oxidizing agents that tend to exothermic decomposition and explosion, and cannot be handled in their pure form without protective measures.
  • Belgian patent 560 389 describes the stabilization of solid peroxycarboxylic acids with the aid of hydratable inorganic salts, whereby granulation is also possible.
  • the conversion into the granulated form is particularly desirable when the percarboxylic acids are to be mixed with other components, but which, for. B. may not come into direct contact with the peracids because of their sensitivity to oxidation.
  • German Offenlegungsschrift 2,422,691 mentions a special embodiment of the stabilization with salts, in which mixtures of magnesium sulfate with little sodium or potassium sulfate are used.
  • the measures described have solved a number of problems with the use of peroxycarboxylic acids, it has so far been far from a percarboxylic acid formulation which meets all requirements for safe handling, mechanical and chemical stability. Solubility and economical production.
  • the granules of peracids and inorganic salts are sufficiently desensitized forms; however, they are only slightly resistant to abrasion, so that in many cases it is not possible to prevent the release of the peroxycarboxylic acids from the granules during storage and thus the oxidation of other sensitive components of the bleaching preparations which contain these granules.
  • coating substances improves the mechanical properties of the granules and reduces the interaction with other components, but has other disadvantages, such as poor chemical stability with some hydrophilic coating substances or impairment of dissolution in water with hydrophobic coatings or those made from anhydrous surfactants.
  • the object of the present invention was to find a preparation form of solid aliphatic peroxycarboxylic acids which is improved compared to the prior art.
  • a bleaching agent in the form of a uniformly composed granulate which contains an aliphatic peroxycarboxylic acid having 4 to 36 C atoms and a hydratable inorganic salt which is solid at room temperature and which is characterized in that it contains 3 to 50% by weight of such peroxycarboxylic acid, 40 to 95% by weight, based on the anhydrous form, of hydratable inorganic salt and 0.2 to 10% by weight of an organic polymer compound which is soluble in an alkaline aqueous medium as a granulating aid - although if microfine starch is contained, the granules are free of microcrystalline cellulose -, all components are evenly distributed in the individual granules of the granules and the granules alone in 0.5% in water give a pH in the range from 3 to 7.
  • This peroxycarboxylic acid formulation is a sufficiently desensitized, abrasion-resistant and dust-free and therefore easy to handle form of the solid aliphatic peracids.
  • the granules quickly dissolve in water or an alkaline aqueous medium, so that the peracids contained without delay as bleaching agents in the Fleet are available.
  • the peracids are chemically unusually stable in this form and can therefore be stored for a long time even under unfavorable conditions.
  • the granules can be produced in a simple manner by means of build-up granulation in a one-step process.
  • the peracid granules according to the invention can generally be used wherever the percarboxylic acids contained can advantageously be used as oxidizing agents, bleaching agents or disinfectants.
  • the preferred field of application is fiber and textile bleaching, and here in particular the bleaching of textiles in the washing process.
  • a particular advantage of the granules is their compatibility with other detergent constituents, in particular alkaline substances and oxidation-sensitive components, which makes it possible to mix the peracids with the detergents without further measures and to store them in this form.
  • Monoperoxycarboxylic acids with 10 - 18 C are particularly preferred -Atoms and the diperoxycarboxylic acids with 6 - 22 C atoms, of which in turn the unbranched a, m-diperoxydicarboxylic acids with 9 - 13 C atoms are of outstanding importance because of their particularly good bleaching action.
  • the peroxycarboxylic acids should be solid as pure compounds at room temperature, in particular up to 50 ° C. Particularly preferred are those peracids which are also solid in technical quality, ie, with a clear content of the underlying carboxylic acid up to 50 ° C.
  • the content of peracids in the granules is 3 to 50 percent by weight, preferably 5 to 30 percent by weight, and in particular 7 to 20 percent by weight.
  • Suitable hydratable inorganic salts for the granules according to the invention are salts of sodium, potassium, magnesium, calcium and aluminum with oxidation-stable anions of mineral acids, insofar as these salts can form defined hydrates and do not react alkaline in water.
  • Examples of such salts are NaH 2 PO 4 and KAI (SO 4 ) 2 - preferably sodium sulfate and magnesium sulfate are used; a mixture of sodium sulfate and magnesium sulfate in a ratio of 2: 1 to 40: 1, preferably 5: 1 to 25: 1 (based on the anhydrous forms) is particularly preferred.
  • the content of inorganic salt in the granules is 40-95 percent by weight, preferably 70-92 percent by weight, but in particular 75-90 percent by weight, also based on the anhydrous form of the salt.
  • the granulation aid is of particular importance.
  • Organic polymer compounds which are soluble in an alkaline aqueous medium such as soluble cellulose or starch derivatives or soluble, fully synthetic polymers, are suitable. Examples include methyl cellulose, solid polyethylene oxides, polyvinyl pyrrolidone and polymeric carboxylic acids.
  • the homopolymers of acrylic acid, maleic acid and crotonic acid and their copolymers are preferably used with one another and with other monomers, in particular polyacrylic acid, maleic acid / acrylic acid copolymers (molar ratio 1: 5 to 5: 1) and crotonic acid / vinyl acetate copolymers (molar ratio 1:10 to 1:80), which deliver particularly high-quality peracid granules.
  • Polymers containing carboxyl groups are preferably in the acid form, but can also be used partially as salts, provided they do not react in an alkaline manner.
  • the amount of polymeric granulation aid is 0.2-10 percent by weight and in particular 0.5-4 percent by weight of the finished bleaching agent.
  • the granulation auxiliaries in the amounts used do not impair the chemical stability of the peracids, so that the bleaching activity of the products is largely retained even when stored for a long time.
  • various additives can often increase stability.
  • chelating agents for heavy metals in particular in amounts of up to 2 percent by weight, preferably 0.1-1 percent by weight, can have an advantageous effect on the maintenance of the active oxygen during storage and / or during the bleaching process in solution.
  • All complexing agents customary for the stabilization of peroxycarboxylic acids can be used; but preferably polyphosphonic acids, such as 1-hydroxyethane-1,1-diphosphonic acid or ethylenediaminetetramethylenephosphonic acid, and their salts are used.
  • surfactants do not adversely affect the storage stability of the granules even if they are incorporated evenly into the grains.
  • These are certain anionic surfactants, namely the salts of long-chain monoalkylsulfuric acid esters (alcohol sulfates), in particular the fatty alcohol sulfates and the salts of sulfuric acid semiesters of the reaction products from long-chain alcohols, in particular from fatty alcohols, with ethylene oxide (ether sulfates).
  • these surfactants seem to improve storage stability in some cases and have a positive effect on the bleaching results that can be achieved with the granules.
  • the proportion of these surfactants in the granules can be up to 10 percent by weight; it is preferably between 1 and 5 percent by weight.
  • the finished granulated bleaching agents contain water in amounts of up to 20 percent by weight, preferably in amounts between 0.5 and 5 percent by weight.
  • the amount of water contained is always smaller than the amount that can be calculated as the maximum possible proportion of hydrate water from the salt content of the granules.
  • the water content of the granules is due to the manufacturing process. The presence of water has an advantageous effect on the desensitization of peracids, but it is not absolutely necessary for this purpose.
  • Granulation processes are suitable for the production of the granules, in which strong thermal and mechanical loads which could lead to the decomposition of the peracids are avoided.
  • Build-up granulation methods such as fluidized bed granulation, roll granulation in rotating drums or on granulation plates and mixed granulation, of which in turn the mixed granulation method, in particular in mixers with rotating tools, such as e.g. B. the Patterson-Kelly mixer, the Lödige mixer and the Forberg mixer, are particularly preferred.
  • premixes which can be handled safely, such as those used in the production of the percarboxylic acids, e.g. B. acc. To German Offenlegungsschrift 2 930 546.
  • Such premixes contain, based on dry matter, about 10 to 90 percent by weight of the solid aliphatic peroxycarboxylic acid, in addition to this, portions of the underlying carboxylic acid (due to insufficient conversion during conversion into the peracid), traces of hydrogen peroxide and inorganic salts, in particular Na 2 S0 4 and MgSO 4 .
  • these peracid premixes do not have to be dried in order to produce the granules according to the invention, but can be used in a moist form, such as is initially obtained during production.
  • the water content of the premixes can also be above the maximum amount that can be fixed in the salts as water of hydration.
  • the solid peracid or, preferably, the peracid premix with other solid constituents of the granules are introduced into the granulation apparatus, for example a Patterson-Kelly V mixer or a Lödige ploughshare mixer, and premixed intensively.
  • Water or a solution or suspension of granulate constituents in water, preferably an aqueous solution of the granulating aid is then introduced in finely divided form with constant movement and the movement of the apparatus is continued until a uniform distribution of all constituents has occurred and the desired particle size range of the granules has formed Has.
  • the amount of water is preferably chosen so that the wet granules formed primarily have between 8 and 30 percent by weight water.
  • the starting materials already contain enough water metering in during the course of the granulation can also be dispensed with.
  • the mixed granulation described can take place at room temperature, but also at a slightly elevated temperature of up to about 45 ° C., preferably between 32 and 40 ° C.
  • the granulation can be followed by drying of the granules, which can optionally be carried out in the same apparatus, but also with the aid of other gentle processes, for example in a fluidized bed process. Post-dried granules are particularly preferred when it comes to a if possible ballast-free peracid formulation arrives. If the granules are obtained by a process which provides a very broad particle size distribution, screening of the finished material and recycling of the undesired particle sizes, if appropriate after grinding, may be appropriate.
  • the resulting peracid granules are characterized by high mechanical stability, in particular by resistance to abrasion. They can be produced in various grain sizes, especially in the range 0.1 to 5 mm. The range from 0.4 to 1.6 mm is of particular importance for incorporation into detergent, while coarser granules with grain sizes in the range from 1.6 to 4 mm can also be preferred for independently used special products.
  • the granules according to the invention generally have bulk densities between 400 and 1200 grams per liter, preferably between 500 and 1000 g / l.
  • a particularly preferred area of application of the bleaching agents according to the invention is the bleaching of textiles in connection with a washing treatment.
  • the granules can be used for this purpose in a uniform form, i.e. without further admixtures, but they are preferably made up as sprinkle-free mixtures with other solid active substances which are necessary for textile treatment.
  • a bleaching agent based on the granules according to the invention can, for example, contain alkalizing agents as further active ingredients.
  • Peracid activators and optionally other bleaching agents, such as perborate contain.
  • For a combined detergent and bleaching agent furthermore, in particular surfactants, builders, foam-suppressing substances and optical brighteners should be mentioned as active ingredients.
  • the excellent mechanical and chemical stability of the granules and their compatibility with the surrounding materials have a particularly advantageous effect, in particular on the storage stability of the finished products.
  • Example 2 In the same mixer as in Example 1 were 0.69 kg of a dry desensitized diperdodecanedioic acid (content in wt .-% peracid 34; Na 2 S0 4 63; dodecanedioic 3), 1.08 kg of dry Na z S0 4, 0.23 kg of MgSO 4 .H 2 0 (water content 30% by weight) and 33 g of powdery polyacrylic acid (molecular weight approx. 1000) are introduced and premixed at 20 rpm in 2 minutes. 0.325 kg of water were then injected via the spray wave within 1 min. The resulting wet granules were dried in the fluidized bed for 30 minutes (air flow approx. 2 m 3 / min, 40 ° C.). For analysis data see table 1.
  • the bleaching tests were carried out in household drum washing machines at a liquor temperature of at most 30 ° C. and a washing time of 15 minutes, so that differences in the dissolving behavior of the granules were particularly evident.
  • the wash liquor (20 l per machine) contained 120 g of a detergent of the following composition:

Abstract

1. A bleaching agent in the form of a granulate of uniform composition which contains an aliphatic C4 -C36 peroxycarboxylic acid solid at room temperature and hydratable inorganic salt, characterized in that it contains 3 to 50% by weight of the peroxycarboxylic acid, 40 to 95% by weight, based on the anhydrous form, of hydratable inorganic salt and 0.2 to 10% by weight of an organic polymer compound soluble in alkaline-aqueous medium as granulation aid, the granulate being free from microcrystalline cellulose where microfine starch is present, all the components are uniformly distributed in the individual grains of the granulate and the granulates alone, 0.5% in water, have a pH value in the range from 3 to 7.

Description

Die vorliegende Erfindung betrifft Bleichwirkstoffe in granulierter Form, die als Bleichkomponente feste aliphatische Peroxycarbonsäure enthalten.The present invention relates to bleaching agents in granular form which contain solid aliphatic peroxycarboxylic acid as the bleaching component.

Auf dem Gebiet der Textilbleiche werden in großem Umfang Bleichmittel auf Basis von Persauerstoffverbindungen eingesetzt. Weite Verbreitung haben insbesondere Wasserstoffperoxid und seine anorganischen Derivate, wie Natriumperborat und Natriumpercarbonat gefunden, die einerseits sehr sicher handhabbare, milde Oxidationsmittel darstellen und andererseits bei genügend hohen Temperaturen ein gutes Bleichvermögen besitzen. Für den Einsatz bei niedrigeren Temperaturen werden dagegen, um eine Bleiche in ausreichend kurzer Zeit zu erreichen, stärkere Oxidationsmittel, wie etwa Peroxycarbonsäuren, benötigt. Peroxycarbonsäuren, auch kürzer als Percarbonsäuren oder einfach Persäuren bezeichnet, sind jedoch sehr aggressive Oxidationsmittel, die zur exothermen Zersetzung und Explosion neigen, und können in reiner Form nicht ohne Schutzvorkehrungen gehandhabt werden. Es ist deshalb u.a. vorgeschlagen worden, um diese Nachteile zu vermeiden, diese Verbindungen erst in situ aus den ungefährlichen anorganischen Perverbindungen und bestimmten Acylierungsmitteln, sogenannten Aktivatoren, zu erzeugen, die als solche keine exotherme Zersetzung oder Oxidationsreaktionen zeigen, sondern allenfalls hydrolyseempfindlich sind. Dieses Verfahren ist durch die Verwendung von zwei getrennt zu dosierenden Komponenten aufwendig, und zudem erfordert die Aktivierungsreaktion zwischen anorganischen Perverbindungen und Aktivatoren vor allem bei sehr niedrigen Arbeitstemperaturen eine unter Umständen unerwünscht lange Vorlaufzeit.Bleaching agents based on peroxygen compounds are widely used in the field of textile bleaching. In particular, hydrogen peroxide and its inorganic derivatives, such as sodium perborate and sodium percarbonate, have found widespread use, which on the one hand are very safe to handle, mild oxidizing agents and on the other hand have a good bleaching capacity at sufficiently high temperatures. For use at lower temperatures, however, stronger oxidizing agents, such as peroxycarboxylic acids, are required in order to achieve bleaching in a sufficiently short time. Peroxycarboxylic acids, also called percarboxylic acids or simply peracids, are very aggressive oxidizing agents that tend to exothermic decomposition and explosion, and cannot be handled in their pure form without protective measures. It is therefore among other things In order to avoid these disadvantages, it has been proposed to produce these compounds only in situ from the harmless inorganic per-compounds and certain acylating agents, so-called activators, which as such do not show any exothermic decomposition or oxidation reactions, but are at most sensitive to hydrolysis. This process is complex due to the use of two components to be metered separately, and moreover the activation reaction between inorganic per-compounds and activators requires an undesirably long lead time, especially at very low working temperatures.

Aus diesen Gründen ist man seit langem bemüht, geeignete Maßnahmen zu finden, die es erlauben, Percarbonsäuren trotz ihrer Instabilität und aggressiven chemischen Eigenschaften als solche zum Bleichen von Textilien zu verwenden. Besonders für die Anwendung in Kombination mit Waschverfahren hat sich dabei das Interesse auf die festen Percarbonsäuren gerichtet.For these reasons, efforts have long been made to find suitable measures which make it possible to use percarboxylic acids as such for bleaching textiles, despite their instability and aggressive chemical properties. In particular for use in combination with washing processes, interest has turned to solid percarboxylic acids.

So beschreibt die belgische Patentschrift 560 389 die Stabilisierung von festen Peroxycarbonsäuren mit Hilfe von hydratisierbaren anorganischen Salzen, wobei auch eine Granulierung möglich ist. Die Überführung in die granulierte Form ist insbesondere dann erwünscht, wenn die Percarbonsäuren noch mit anderen Komponenten gemischt werden sollen, die aber z. B. wegen ihrer Oxidationsempfindlichkeit nicht in direkten Kontakt mit den Persäuren kommen dürfen. Die deutsche Offenlegungsschrift 2 422 691 erwähnt eine besondere Ausgestaltung der Stabilisierung mit Salzen, bei der Gemische aus Magnesiumsulfat mit wenig Natrium- oder Kaliumsulfat verwendet werden.Belgian patent 560 389 describes the stabilization of solid peroxycarboxylic acids with the aid of hydratable inorganic salts, whereby granulation is also possible. The conversion into the granulated form is particularly desirable when the percarboxylic acids are to be mixed with other components, but which, for. B. may not come into direct contact with the peracids because of their sensitivity to oxidation. German Offenlegungsschrift 2,422,691 mentions a special embodiment of the stabilization with salts, in which mixtures of magnesium sulfate with little sodium or potassium sulfate are used.

Unter Zusatz eines Gemisches von mikrofeiner Stärke und mikrokristalliner Cellulose sind Percarbonsäuren zusammen mit Natriumsulfat auch schon zu Tabletten verpreßt worden (US-A-4 013 581).With the addition of a mixture of microfine starch and microcrystalline cellulose, percarboxylic acids have also been pressed together with sodium sulfate to give tablets (US Pat. No. 4,013,581).

Eine andere Maßnahme zur Verhinderung unerwünschter Wechselwirkungen zwischen Peroxycarbonsäuren und anderen Komponenten stellt die Umhüllung von Persäureteilchen dar. In der französischen Patentschrift 1 262 475 werden hierzu hydrophile Filmbildner, wie Gelatine, verwendet. In der britischen Patentschrift 1 387 167 wird vorgeschlagen, wasserundurchlässige Materialien, wie Fette und Wachse, zur Umhüllung einzusetzten. Eine weitere Variante bietet die deutsche Offenlegungsschrift 2 737 864, in der Tenside als Überzugsmaterialien vorgeschlagen werden.Another measure for preventing undesirable interactions between peroxycarboxylic acids and other components is the encapsulation of peracid particles. In French patent specification 1,262,475, hydrophilic film formers, such as gelatin, are used for this purpose. British Patent 1,387,167 proposes the use of water-impermeable materials, such as fats and waxes, for wrapping. A further variant is offered by German Offenlegungsschrift 2,737,864, in which surfactants are proposed as coating materials.

Weiterhin sind zahlreiche Vorschläge gemacht worden, die Phlegmatisierung durch Salzhydrate mit dem Umhüllungsverfahren zu verbinden. So beispielsweise in der deutschen Offenlegungsschrift 2 422 735, in der ein Gemisch zweier Granulate beschrieben wird, von denen eines aus Salzhydrate enthaltenden, mit Fettalkohol überzogenen Percarbonsäureteilchen besteht. Ähnliche Granulate beschreiben die US-Patentschriften 3 770 816 und 4 170 453 und die deutsche Offenlegungsschrift 2 652 424. Die US-Patentschrift 4 259 201 gibt ein Beispiel für die Verwendung salzhaltiger, mit Tensiden überzogener Persäuregranulate in Waschmitteln.Furthermore, numerous proposals have been made to combine the desensitization by salt hydrates with the coating process. For example, in German Offenlegungsschrift 2,422,735, which describes a mixture of two granules, one of which consists of percarboxylic acid particles containing salt hydrates and coated with fatty alcohol. Similar granules are described in US Pat. Nos. 3,770,816 and 4,170,453 and German Offenlegungsschrift 2,652,424. US Pat. No. 4,259,201 provides an example of the use of saline-containing peracid granules in detergents.

Obwohl durch die beschriebenen Maßnahmen eine Reihe von Problemen beim Einsatz der Peroxycarbonsäuren gelöst worden sind, war man bisher noch weit von einer Percarbonsäureformulierung entfernt, die allen Anforderungen an gefahrlose Handhabbarkeit, mechanische und chemische Stabilität. Löslichkeit und wirtschaftliche Herstellung gerecht wird. So stellen die Granulate aus Persäuren und anorganischen Salzen zwar hinreichend phlegmatisierte Formen dar; sie sind aber nur wenig abriebfest, so daß es in vielen Fällen nicht gelingt, die Freisetzung der Peroxycarbonsäuren aus den Granulaten während der Lagerung und damit die Oxidation anderer empfindlicher Komponenten der Bleichzubereitungen, die diese Granulate enthalten, zu verhindern. Die Anwendung von Hüllsubstanzen verbessert zwar die mechanischen Eigenschaften der Granulate und verringert die Wechselwirkung mit anderen Komponenten, bringt aber andere Nachteile mit sich, wie geringe chemische Stabilität bei einigen hydrophilen Hüllsubstanzen oder Behinderung der Auflösung in Wasser bei hydrophoben Überzügen oder solchen aus wasserfreien Tensiden.Although the measures described have solved a number of problems with the use of peroxycarboxylic acids, it has so far been far from a percarboxylic acid formulation which meets all requirements for safe handling, mechanical and chemical stability. Solubility and economical production. For example, the granules of peracids and inorganic salts are sufficiently desensitized forms; however, they are only slightly resistant to abrasion, so that in many cases it is not possible to prevent the release of the peroxycarboxylic acids from the granules during storage and thus the oxidation of other sensitive components of the bleaching preparations which contain these granules. The use of coating substances improves the mechanical properties of the granules and reduces the interaction with other components, but has other disadvantages, such as poor chemical stability with some hydrophilic coating substances or impairment of dissolution in water with hydrophobic coatings or those made from anhydrous surfactants.

Man ist deshalb nach wie vor bemüht, neue Persäureformulierungen mit ingesamt besseren Eigenschaften zu finden, und versucht dabei u.a., die Abhängigkeit der Stabilität von der Art der zugesetzten Hilfsstoffe zu ergründen. So haben sich viele Komplexbildner, die in der Lage sind, Schwermetalle zu maskieren, bei nahezu allen Peroxycarbonsäuren als Stabilisatoren gegen katalytische Zersetzung bewährt, während z. B. bei bestimmten Peroxycarbonsäuren, wie in der US-Patentschrift 3 639 285 erwähnt wird, Tenside die Zersetzung fördern. Bei anderen Peroxycarbonsäuren wiederum wirken, wie aus der europäischen Offenlegungsschrift 74 730 hervorgeht, bestimmte Überzugsmittel destabilisierend. Aufgrund dieser und weiterer ähnlicher Ergebnisse scheint sich heute die Auffassung durchzusetzen, daß sich die Erfahrungen mit einem Persäuretyp nur selten auf einen anderen Typ übertragen lassen. Optimale Formulierungen sind danach nur durch Maßnahmen zu erreichen, die auf den jeweiligen Typ von Percarbonsäure individuell zugeschnitten sind.Therefore, efforts are still being made to find new peracid formulations with overall better properties, and attempts are being made to investigate, inter alia, the dependence of stability on the type of auxiliary substances added. So many complexing agents, which are able to mask heavy metals, have proven themselves with almost all peroxycarboxylic acids as stabilizers against catalytic decomposition, while e.g. B. in certain peroxycarboxylic acids, as mentioned in US Pat. No. 3,639,285, surfactants promote decomposition. In the case of other peroxycarboxylic acids, as is evident from European laid-open specification 74 730, certain coating agents have a destabilizing effect. Based on these and other similar results, it now seems to be accepted that experience with one type of peracid can rarely be transferred to another type. According to this, optimal formulations are only possible through measures achieve that are individually tailored to the respective type of percarboxylic acid.

Der vorliegenden Erfindung lag in diesem Zusammenhang die Aufgabe zugrunde, eine gegenüber dem Stand der Technik verbesserte Zubereitungsform von festen aliphatischen Peroxycarbonsäuren zu finden.In this connection, the object of the present invention was to find a preparation form of solid aliphatic peroxycarboxylic acids which is improved compared to the prior art.

Diese Aufgabe wird erfindungsgemäß gelöst durch einen Bleichwirkstoff in Form eines einheitlich zusammengesetzten Granulates, der eine bei Raumtemperatur feste aliphatische Peroxycarbonsäure mit 4 bis 36 C-Atomen und hydratisierbares anorganisches Salz enthält und der dadurch gekennzeichnet ist, daß er 3 bis 50 Gew.-% an solcher Peroxycarbonsäure, 40 bis 95 Gew.-%, bezogen auf die wasserfreie Form, an hydratisierbarem anorganischem Salz und 0,2 bis 10 Gew.-% einer organischen, in alkalisch-wäßrigem Milieu löslichen Polymerverbindung als Granulierhilfsmittel enthält - wobei, wenn mikrofeine Stärke enthalten ist, das Granulat frei ist von mikrokristalliner Cellulose - , alle Komponenten gleichmäßig in den einzelnen Körnern des Granulates verteilt sind und die Granulate allein 0,5 %-ig in Wasser einen pH-Wert im Bereich von 3 bis 7 ergeben.This object is achieved according to the invention by a bleaching agent in the form of a uniformly composed granulate which contains an aliphatic peroxycarboxylic acid having 4 to 36 C atoms and a hydratable inorganic salt which is solid at room temperature and which is characterized in that it contains 3 to 50% by weight of such peroxycarboxylic acid, 40 to 95% by weight, based on the anhydrous form, of hydratable inorganic salt and 0.2 to 10% by weight of an organic polymer compound which is soluble in an alkaline aqueous medium as a granulating aid - although if microfine starch is contained, the granules are free of microcrystalline cellulose -, all components are evenly distributed in the individual granules of the granules and the granules alone in 0.5% in water give a pH in the range from 3 to 7.

Diese Peroxycarbonsäureformulierung stellt eine ausreichend phlegmatisierte, abriebfeste und staubfreie und somit gut handhabbare Form der festen aliphatischen Persäuren dar. Trotz der hohen mechanischen Stabilität lösen sich die Granulate schnell in Wasser oder alkalisch-wäßrigem Milieu, so daß die enthaltenen Persäuren ohne Verzögerung als Bleichmittel in der Flotte zur Verfügung stehen. Die Persäuren sind in dieser Form chemisch ungewöhnlich stabil und deshalb auch unter ungünstigen Bedingungen lange lagerbar. Weiterhin ist die Herstellung der Granulate auf einfachem Wege durch Aufbaugranulierung in einem einstufigen Prozeß möglich.This peroxycarboxylic acid formulation is a sufficiently desensitized, abrasion-resistant and dust-free and therefore easy to handle form of the solid aliphatic peracids. Despite the high mechanical stability, the granules quickly dissolve in water or an alkaline aqueous medium, so that the peracids contained without delay as bleaching agents in the Fleet are available. The peracids are chemically unusually stable in this form and can therefore be stored for a long time even under unfavorable conditions. Furthermore, the granules can be produced in a simple manner by means of build-up granulation in a one-step process.

Die erfindungsgemäßen Persäuregranulate lassen sich generell überall dort verwenden, wo die enthaltenen Percarbonsäuren als Oxidations-, Bleich- oder Desinfektionsmittel vorteilhaft eingesetzt werden können. Bevorzugtes Anwendungsgebiet ist aber die Faser- und Textilbleiche und hier insbesondere die Bleiche von Textilien im Waschprozeß. Dabei wirkt sich als besonderer Vorteil der Granulate ihre Verträglichkeit mit anderen Waschmittelbestandteilen, insbesondere alkalisch reagierenden Substanzen und oxidationsempfindlichen Komponenten aus, die es ermöglicht, die Persäuren ohne weitere Maßnahmen mit den Waschmitteln zu mischen und in dieser Form zu lagern.The peracid granules according to the invention can generally be used wherever the percarboxylic acids contained can advantageously be used as oxidizing agents, bleaching agents or disinfectants. However, the preferred field of application is fiber and textile bleaching, and here in particular the bleaching of textiles in the washing process. A particular advantage of the granules is their compatibility with other detergent constituents, in particular alkaline substances and oxidation-sensitive components, which makes it possible to mix the peracids with the detergents without further measures and to store them in this form.

Bei den in den erfindungsgemäßen Bleichwirkstoffen enthaltenen Peroxycarbonsäuren handelt es sich um feste aliphatische Verbindungen mit 4 bis 36 C-Atomen, die ein- oder mehrmals im Molekül an Kohlenstoff gebunden die Gruppe -C03H aufweisen. Sie können gegebenenfalls als Substituenten die Gruppen -C02H, -C02Me, -S03H und -S03Me oder Ethersauerstoffe enthalten, wobei Me ein Äquivalent eines Metallkations aus der Gruppe Na+, K+, Mg2+ und Ca2+ bedeutet, sind aber vorzugsweise nicht substituierte Verbindungen der Formel C(n.x)H(2n+2-3x)(C03H)x mit n = 4 bis 36 und x = 1 bis 3. Besonders bevorzugt werden die Monoperoxycarbonsäuren mit 10 - 18 C-Atomen und die Diperoxycarbonsäuren mit 6 - 22 C-Atomen, von denen wiederum die unverzweigten a,m-Diperoxydicarbonsäuren mit 9 - 13 C-Atomen herausragende Bedeutung wegen ihrer besonders guten Bleichwirkung besitzen. Die Peroxycarbonsäuren sollen als reine Verbindungen bei Raumtemperatur, insbesondere bis 50°C, fest sein. Besonders bevorzugt werden solche Persäuren, die auch in technischer Qualität, d. h., mit einem deutlichen Gehalt an der zugrunde liegenden Carbonsäure bis 50°C fest sind. Der Gehalt an Persäuren in den Granulaten beträgt 3 - 50 Gewichtsprozent, vorzugsweise 5 - 30 Gew.-%, und insbesondere 7 - 20 Gew.-%.The peroxycarboxylic acids contained in the bleaching agents according to the invention are solid aliphatic compounds having 4 to 36 carbon atoms which have the group —C0 3 H bonded to carbon one or more times in the molecule. They may optionally contain the groups -C0 2 H, -C0 2 Me, -S0 3 H and -S0 3 Me or ether oxygen, where Me is an equivalent of a metal cation from the group Na + , K +, Mg 2 + and Ca 2 + means, but are preferably unsubstituted compounds of the formula C (nx) H (2n + 2-3x) (C03H) x with n = 4 to 36 and x = 1 to 3. Monoperoxycarboxylic acids with 10 - 18 C are particularly preferred -Atoms and the diperoxycarboxylic acids with 6 - 22 C atoms, of which in turn the unbranched a, m-diperoxydicarboxylic acids with 9 - 13 C atoms are of outstanding importance because of their particularly good bleaching action. The peroxycarboxylic acids should be solid as pure compounds at room temperature, in particular up to 50 ° C. Particularly preferred are those peracids which are also solid in technical quality, ie, with a clear content of the underlying carboxylic acid up to 50 ° C. The content of peracids in the granules is 3 to 50 percent by weight, preferably 5 to 30 percent by weight, and in particular 7 to 20 percent by weight.

Als hydratisierbare anorganische Salze eignen sich für die erfindungsgemäßen Granulate Salze des Natriums, Kaliums, Magnesiums, Calciums und Aluminiums mit oxidationsstabilen Anionen von Mineralsäuren, soweit diese Salze definierte Hydrate bilden können und in Wasser nicht alkalisch reagieren. Beispiele solcher Salze sind NaH2P04 und KAI(SO4)2- Vorzugsweise werden Natriumsulfat und Magnesiumsulfat verwendet; besonders bevorzugt wird dabei eine Mischung von Natriumsulfat und Magnesiumsulfat im Verhältnis von 2 : 1 bis 40 : 1, vorzugsweise 5 : 1 bis 25 : 1 (bezogen auf die wasserfreien Formen). Der Gehalt an anorganischem Salz beträgt in den Granulaten 40 - 95 Gewichtsprozent, vorzugsweise 70 - 92 Gewichtsprozent, insbesondere aber 75 - 90 Gewichtsprozent, ebenfalls bezogen auf die wasserfreie Form des Salzes.Suitable hydratable inorganic salts for the granules according to the invention are salts of sodium, potassium, magnesium, calcium and aluminum with oxidation-stable anions of mineral acids, insofar as these salts can form defined hydrates and do not react alkaline in water. Examples of such salts are NaH 2 PO 4 and KAI (SO 4 ) 2 - preferably sodium sulfate and magnesium sulfate are used; a mixture of sodium sulfate and magnesium sulfate in a ratio of 2: 1 to 40: 1, preferably 5: 1 to 25: 1 (based on the anhydrous forms) is particularly preferred. The content of inorganic salt in the granules is 40-95 percent by weight, preferably 70-92 percent by weight, but in particular 75-90 percent by weight, also based on the anhydrous form of the salt.

Besondere Bedeutung kommt dem Granulierhilfsmittel zu. Geeignet sind organische, in alkalisch-wäßrigem Milieu lösliche Polymerverbindungen wie lösliche Cellulose- oder Stärkederivate oder lösliche, vollsynthetische Polymere. Als Beispiele seien Methylcellulose, feste Polyethylenoxide, Polyvinylpyrrolidon und polymere Carbonsäuren genannt. Vorzugsweise werden die Homopolymerisate von Acrylsäure, Maleinsäure und Crotonsäure und deren Copolymerisate untereinander und mit anderen Monomeren verwendet, insbesondere Polyacrylsäure, Maleinsäure - Acrylsäure - Copolymerisate (Molverhältnis 1 : 5 bis 5 : 1) und Crotonsäure - Vinylacetat - Copolymerisate (Molverhältnis 1 : 10 bis 1 : 80), die besonders hochwertige Persäuregranulate liefern. Carboxylgruppen enthaltende Polymere liegen vorzugsweise in der Säureform vor, können aber auch partiell als Salze eingesetzt werden, sofern diese nicht alkalisch reagieren. Die Menge an polymerem Granulierhilfsmittel beträgt 0,2 - 10 Gewichtsprozent und insbesondere 0,5 - 4 Gewichtsprozent des fertigen Bleichwirkstoffes.The granulation aid is of particular importance. Organic polymer compounds which are soluble in an alkaline aqueous medium, such as soluble cellulose or starch derivatives or soluble, fully synthetic polymers, are suitable. Examples include methyl cellulose, solid polyethylene oxides, polyvinyl pyrrolidone and polymeric carboxylic acids. The homopolymers of acrylic acid, maleic acid and crotonic acid and their copolymers are preferably used with one another and with other monomers, in particular polyacrylic acid, maleic acid / acrylic acid copolymers (molar ratio 1: 5 to 5: 1) and crotonic acid / vinyl acetate copolymers (molar ratio 1:10 to 1:80), which deliver particularly high-quality peracid granules. Polymers containing carboxyl groups are preferably in the acid form, but can also be used partially as salts, provided they do not react in an alkaline manner. The amount of polymeric granulation aid is 0.2-10 percent by weight and in particular 0.5-4 percent by weight of the finished bleaching agent.

Durch den Einsatz der vorgenannten Granulierhilfsmittel ist es möglich, die Gemische aus Persäuren und Salzen mit Hilfe kleiner Mengen dieser Zusatzstoffe in mechanisch stabile Granulate zu überführen, ohne eine Umhüllung der Körner durchführen zu müssen. Auf diese Weise wird die Herstellung stabiler Persäuregranulate vereinfacht und gleichzeitig werden die Nachteile der umhüllten Produkte, vor allem der langsame Zerfall der Körner in der Bleichflotte, vermieden. Durch die gleichmäßige Verteilung aller Komponenten in den einzelnen Körnern und die Anwesenheit der Granulierhilfsmittel scheint darüberhinaus die Dispergierung und Auflösung der in den Granulaten enthaltenen Persäurepartikel in der Flotte sogar begünstigt zu werden. Besonders vorteilhaft wirkt sich hier der Einsatz von nur im alkalischen Medium löslichen GranulierhilfsmitteIn, beispielsweise den Crotonsäure - Vinylacetat - Copolymeren, aus.By using the aforementioned granulation aids, it is possible to convert the mixtures of peracids and salts with the aid of small amounts of these additives into mechanically stable granules without having to carry out a coating of the grains. In this way, the production of stable peracid granules is simplified and at the same time the disadvantages of the coated products, especially the slow disintegration of the grains in the bleaching liquor, are avoided. Due to the uniform distribution of all components in the individual grains and the presence of the granulation aids, the dispersion and dissolution of the peracid particles contained in the granules even seems to be favored in the liquor. The use of granulating auxiliaries which are only soluble in the alkaline medium, for example the crotonic acid / vinyl acetate copolymers, has a particularly advantageous effect here.

Überraschenderweise beeinträchtigen die Granulierhilfsmittel in den verwendeten Mengen die chemische Stabilität der Persäuren nicht, so daß die Bleichaktivität der Produkte auch bei langer Lagerung weitgehend erhalten bleibt. Durch verschiedene Zusätze ist allerdings oft noch eine Steigerung der Stabilität möglich. So hat sich gezeigt, daß sich Chelatkomplexbildner für Schwermetalle, insbesondere in Mengen bis zu 2 Gewichtsprozent, vorzugsweise 0,1 - 1 Gewichtsprozent, vorteilhaft auf die Erhaltung des Aktivsauerstoffs während der Lagerung und/oder während des Bleichvorganges in Lösung auswirken können. Verwendbar sind alle für die Stabilisierung von Peroxycarbonsäuren übliche Komplexbildner; vorzugsweise werden aber Polyphosphonsäuren, wie 1-Hydroxyethan-1,1-diphosphonsäure oder Ethylendiamintetramethylenphosphonsäure, und deren Salze eingesetzt.Surprisingly, the granulation auxiliaries in the amounts used do not impair the chemical stability of the peracids, so that the bleaching activity of the products is largely retained even when stored for a long time. However, various additives can often increase stability. It has been shown that chelating agents for heavy metals, in particular in amounts of up to 2 percent by weight, preferably 0.1-1 percent by weight, can have an advantageous effect on the maintenance of the active oxygen during storage and / or during the bleaching process in solution. All complexing agents customary for the stabilization of peroxycarboxylic acids can be used; but preferably polyphosphonic acids, such as 1-hydroxyethane-1,1-diphosphonic acid or ethylenediaminetetramethylenephosphonic acid, and their salts are used.

Weiterhin hat sich überraschenderweise gezeigt, daß bestimmte Tenside die Lagerstabilität der Granulate auch dann nicht negativ beeinflussen, wenn sie gleichmäßig in die Körner eingearbeitet werden. Es handelt sich um bestimmte Aniontenside, nämlich die Salze von langkettigen Monoalkylschwefelsäureestern (Alkoholsulfate), insbesondere die Fettalkoholsulfate und die Salze von Schwefelsäurehalbestern der Umsetzungsprodukte aus langkettigen Alkoholen, insbesondere aus Fettalkoholen, mit Ethylenoxid (Ethersulfate). Diese Tenside scheinen im Gegenteil in einigen Fällen die Lagerstabilität noch zu verbessern und sich positiv auf das mit den Granulaten erzielbare Bleichergebnis auszuwirken. Der Anteil an diesen Tensiden kann in den Granulaten bis zu 10 Gewichtsprozent betragen; er liegt vorzugsweise zwischen 1 und 5 Gewichtsprozent.Furthermore, it has surprisingly been found that certain surfactants do not adversely affect the storage stability of the granules even if they are incorporated evenly into the grains. These are certain anionic surfactants, namely the salts of long-chain monoalkylsulfuric acid esters (alcohol sulfates), in particular the fatty alcohol sulfates and the salts of sulfuric acid semiesters of the reaction products from long-chain alcohols, in particular from fatty alcohols, with ethylene oxide (ether sulfates). On the contrary, these surfactants seem to improve storage stability in some cases and have a positive effect on the bleaching results that can be achieved with the granules. The proportion of these surfactants in the granules can be up to 10 percent by weight; it is preferably between 1 and 5 percent by weight.

Als weiteren fakultativen Bestandteil enthalten die fertigen granulierten Bleichwirkstoffe Wasser in Mengen bis zu 20 Gewichtsprozent, vorzugsweise in Mengen zwischen 0,5 und 5 Gewichtsprozent. Die enthaltene Menge an Wasser ist stets kleiner als die Menge, die sich als maximal möglicher Hydratwasseranteil aus dem Salzgehalt der Granulate errechnen läßt. Der Wassergehalt der Granulate ist fertigungstechnisch bedingt. Auf die Phlegmatisierung der Persäuren wirkt sich die Anwesenheit des Wassers vorteilhaft aus, doch ist sie für diesen Zweck nicht unbedingt erforderlich.As a further optional ingredient, the finished granulated bleaching agents contain water in amounts of up to 20 percent by weight, preferably in amounts between 0.5 and 5 percent by weight. The amount of water contained is always smaller than the amount that can be calculated as the maximum possible proportion of hydrate water from the salt content of the granules. The water content of the granules is due to the manufacturing process. The presence of water has an advantageous effect on the desensitization of peracids, but it is not absolutely necessary for this purpose.

Neben den genannten Komponenten können in die Granulate auch noch andere Bestandteile eingearbeitet werden, sofern sie die positiven Eigenschaften der Grundzusammensetzung nicht negativ beeinflussen. Zu erwähnen sind beispielsweise zusätzliche Phlegmatisierungsmittel, Substanzen zur Modifizierung der Rieselfähigkeit oder der Löslichkeit und Puffersubstanzen. In jedem Falle ist darauf zu achten, daß keine alkalisch reagierenden Materialien verwendet werden und daß die Granulate schwach sauer reagieren. Sie sollen in Wasser (0,5 %-ig) einen pH-Wert zwischen 3 und 7, vorzugsweise zwischen 4 und 6 aufweisen. Die Einhaltung dieser Vorgaben ist wesentlich für die chemische Stabilität der Granulate.In addition to the components mentioned, other constituents can also be incorporated into the granules, provided that they do not negatively influence the positive properties of the basic composition. For example, additional desensitizing agents, substances for modifying the flowability or solubility and buffer substances are to be mentioned. In any case, it must be ensured that no alkaline materials are used and that the granules react weakly acidic. They should have a pH in water (0.5%) of between 3 and 7, preferably between 4 and 6. Compliance with these requirements is essential for the chemical stability of the granules.

Zur Herstellung der Granulate eignen sich Granulationsverfahren, bei denen starke thermische und mechanische Belastungen, die zur Zersetzung der Persäuren führen könnten, vermieden werden. Besonders geeignet sind Aufbaugranulationsverfahren wie die Wirbelschichtgranulation, die Rollgranulation in rotierenden Trommeln oder auf Granuliertellern und die Mischgranulation von denen wiederum die Mischgranulationsverfahren, insbesondere in Mischern mit rotierenden Werkzeugen, wie z. B. dem Patterson-Kelly-Mischer, dem Lödige-Mischer und dem Forberg-Mischer, besonders bevorzugt werden.Granulation processes are suitable for the production of the granules, in which strong thermal and mechanical loads which could lead to the decomposition of the peracids are avoided. Build-up granulation methods such as fluidized bed granulation, roll granulation in rotating drums or on granulation plates and mixed granulation, of which in turn the mixed granulation method, in particular in mixers with rotating tools, such as e.g. B. the Patterson-Kelly mixer, the Lödige mixer and the Forberg mixer, are particularly preferred.

Durch die Herstellung nach den genannten Verfahren wird erreicht, daß in den einzelnen Körnern alle Bestandteile, soweit es ihre Teilchengröße zuläßt, gleichmäßig verteilt sind, und alle Körner gleiche Zusammensetzung haben.It is achieved by the production according to the above-mentioned processes that all constituents, insofar as their particle size permits, are evenly distributed in the individual grains and that all grains have the same composition.

Bei der Herstellung selbst geht man in der Regel nicht von den reinen Percarbonsäuren, sondern von gefahrlos zu handhabenden Vorgemischen aus, wie sie unter anderem bei der Herstellung der Percarbonsäuren, z. B. entsprechend der deutschen Offenlegungsschrift 2 930 546, anfallen. Solche Vorgemische enthalten, bezogen auf Trockensubstanz, etwa 10 bis 90 Gewichtsprozent der festen aliphatischen Peroxycarbonsäure, daneben Anteile der zugrundeliegenden Carbonsäure (infolge unzureichender Umsetzung bei der Überführung in die Persäure), Spuren an Wasserstoffperoxid und anorganische Salze, insbesondere Na2S04 und MgSO4. Als besonderer Vorteil ist es zu werten, daß zur Herstellung der erfindungsgemäßen Granulate diese Persäurevorgemische nicht getrocknet werden müssen, sondern in feuchter Form, wie sie bei der Herstellung zunächst anfallen, eingesetzt werden können. Der Wassergehalt der Vorgemische kann dabei auch über der maximal als Hydratwasser in den Salzen fixierbaren Menge liegen.In the production itself, it is generally not the pure percarboxylic acids that are used, but rather the premixes which can be handled safely, such as those used in the production of the percarboxylic acids, e.g. B. acc. To German Offenlegungsschrift 2 930 546. Such premixes contain, based on dry matter, about 10 to 90 percent by weight of the solid aliphatic peroxycarboxylic acid, in addition to this, portions of the underlying carboxylic acid (due to insufficient conversion during conversion into the peracid), traces of hydrogen peroxide and inorganic salts, in particular Na 2 S0 4 and MgSO 4 . It is a particular advantage that these peracid premixes do not have to be dried in order to produce the granules according to the invention, but can be used in a moist form, such as is initially obtained during production. The water content of the premixes can also be above the maximum amount that can be fixed in the salts as water of hydration.

Im Falle einer Mischgranulation werden die feste Persäure oder, vorzugsweise, das Persäurevorgemisch mit weiteren festen Bestandteilen der Granulate in die Granulationsapparatur, beispielsweise einen Patterson-Kelly V-Mischer oder einen Lödige Pflugscharmischer, eingebracht und intensiv vorgemischt. Unter ständiger Bewegung wird dann in feinverteilter Form Wasser oder eine Lösung oder Suspension von Granulatbestandteilen in Wasser, vorzugsweise eine wäßrige Lösung des Granulierhilfsmittels, eingetragen und die Bewegung der Apparatur fortgesetzt, bis eine gleichmäßige Verteilung aller Bestandteile eingetreten ist und sich das gewünschte Kornspektrum der Granulate gebildet hat. Die Wassermenge wird vorzugsweise so gewählt, daß dieses primär entstehende Feuchtgranulat zwischen 8 und 30 Gewichtsprozent Wasser aufweist. Enthalten die Ausgangsmaterialien bereits genügend Wasser, kann auf die Zudosierung im Verlauf der Granulation auch verzichtet werden. Die beschriebene Mischgranulation kann bei Zimmertemperatur, aber auch bei leicht erhöhter Temperatur bis etwa 45°C, vorzugsweise zwischen 32 und 40°C erfolgen. An die Granulierung kann sich, falls erwünscht, eine Trocknung der Granulate anschließen, die gegebenenfalls in der selben Apparatur, aber auch mit Hilfe anderer schonender Verfahren, beispielsweise in einem Wirbelschichtverfahren, vorgenommen werden kann. Nachgetrocknete Granulate werden vor allem dann bevorzugt, wenn es auf eine möglichst ballastfreie Persäureformulierung ankommt. Werden die Granulate nach einen Verfahren gewonnen, das eine sehr breite Kornverteilung liefert, kann eine Siebung des fertigen Materials und eine Rückführung der unerwünschten Korngrößen, gegebenenfalls nach Mahlen, angebracht sein.In the case of mixed granulation, the solid peracid or, preferably, the peracid premix with other solid constituents of the granules are introduced into the granulation apparatus, for example a Patterson-Kelly V mixer or a Lödige ploughshare mixer, and premixed intensively. Water or a solution or suspension of granulate constituents in water, preferably an aqueous solution of the granulating aid, is then introduced in finely divided form with constant movement and the movement of the apparatus is continued until a uniform distribution of all constituents has occurred and the desired particle size range of the granules has formed Has. The amount of water is preferably chosen so that the wet granules formed primarily have between 8 and 30 percent by weight water. If the starting materials already contain enough water, metering in during the course of the granulation can also be dispensed with. The mixed granulation described can take place at room temperature, but also at a slightly elevated temperature of up to about 45 ° C., preferably between 32 and 40 ° C. If desired, the granulation can be followed by drying of the granules, which can optionally be carried out in the same apparatus, but also with the aid of other gentle processes, for example in a fluidized bed process. Post-dried granules are particularly preferred when it comes to a if possible ballast-free peracid formulation arrives. If the granules are obtained by a process which provides a very broad particle size distribution, screening of the finished material and recycling of the undesired particle sizes, if appropriate after grinding, may be appropriate.

Die resultierenden Persäuregranulate zeichnen sich durch hohe mechanische Stabilität, insbesondere durch Abriebfestigkeit aus. Sie lassen sich in verschiedenen Korngrößen vor allem im Bereich 0,1 bis 5 mm herstellen. Von besonderer Bedeutung für die Einarbeitung in Waschmittel ist dabei der Bereich 0,4 bis 1,6 mm, während für unabhängig eingesetzte Spezialprodukte auch grobere Granulate mit Korngrößen im Bereich von 1,6 bis 4 mm bevorzugt werden können. Die erfindungsgemäßen Granulate besitzen im allgemeinen Schüttgewichte zwischen 400 und 1200 Gramm pro Liter, vorzugsweise zwischen 500 und 1000 g/I.The resulting peracid granules are characterized by high mechanical stability, in particular by resistance to abrasion. They can be produced in various grain sizes, especially in the range 0.1 to 5 mm. The range from 0.4 to 1.6 mm is of particular importance for incorporation into detergent, while coarser granules with grain sizes in the range from 1.6 to 4 mm can also be preferred for independently used special products. The granules according to the invention generally have bulk densities between 400 and 1200 grams per liter, preferably between 500 and 1000 g / l.

Selbstverständlich ist es ohne weiteres möglich, auf die erfindungsgemäßen Granulate nachträglich noch inerte Umhüllungen der verschiedensten Art, sei es in Form geschlossener Filme, sei es in Form abgelagerter feiner Pulver, aufzubringen, doch ist es gerade der Vorzug der vorliegenden Erfindung, ohne eine solche Maßnahme auszukommen.Of course, it is readily possible to apply to the granules according to the invention still inert coatings of various types, whether in the form of closed films or in the form of deposited fine powder, but it is precisely the advantage of the present invention without such a measure get along.

Besonders bevorzugtes Anwendungsgebiet der erfindungsgemäßen Bleichwirkstoffe ist die Bleiche von Textilien im Zusammenhang mit einer Waschbehandlung. Die Granulate können für diesen Zweck in einheitlicher Form, d.h., ohne weitere Zumischungen eingesetzt werden, doch werden sie vorzugsweise als streufähige Gemische mit anderen festen Wirksubstanzen, die für die Textilbehandlung nötig sind, konfektioniert. So kann ein Bleichmittel auf Basis der erfindungsgemäßen Granulate als weitere Wirkstoffe beispielsweise Alkalisierungsmittel. Persäureaktivatoren und gegebenenfalls noch andere Bleichwirkstoffe, wie etwa Perborat, enthalten. Für ein kombiniertes Wasch- und Bleichmittel sind als Wirkstoffe darüberhinaus insbesondere Tenside, Builder, schaumdämpfende Substanzen und optische Aufheller zu erwähnen. In diesen konfektionierten Formen wirkt sich die hervorragende mechanische und chemische Stabilität der Granulate und ihre Verträglichkeit mit den umgebenden Materialien besonders vorteilhaft, insbesondere auf die Lagerstabilität der Fertigprodukte aus.A particularly preferred area of application of the bleaching agents according to the invention is the bleaching of textiles in connection with a washing treatment. The granules can be used for this purpose in a uniform form, i.e. without further admixtures, but they are preferably made up as sprinkle-free mixtures with other solid active substances which are necessary for textile treatment. A bleaching agent based on the granules according to the invention can, for example, contain alkalizing agents as further active ingredients. Peracid activators and optionally other bleaching agents, such as perborate, contain. For a combined detergent and bleaching agent, furthermore, in particular surfactants, builders, foam-suppressing substances and optical brighteners should be mentioned as active ingredients. In these assembled forms, the excellent mechanical and chemical stability of the granules and their compatibility with the surrounding materials have a particularly advantageous effect, in particular on the storage stability of the finished products.

Beispiel 1example 1 Granulat mit Diperoxydodecan-1,12-disäureGranules with diperoxydodecane-1,12-diacid

In einem Patterson-Kelley V-Mischer mit einem Inhalt von 15 I wurden 2,03 kg eines feuchten Filterkuchens (Zusammensetzung in Gewichtsprozent: Diperoxydodecandisäure 29,6; Natriumsulfat 54,8; Dodecandisäure 2,6; Wasser 13), 3,95 kg wasserfreies Natriumsulfat und 0,34 kg Magnesiumsulfat (Wassergehalt 30 Gew.-%) vorgelegt und 1 min lang bei 20 Umdrehungen pro min. vorgemischt. Danach wurden in den sich drehenden Mischbehälter während einer Zeit von 3 min 0,66 kg einer Dispersion eines Crotonsäure-Vinylacetat-Copolymers (Molverhältnis 1 : 17,6; 16 Gew.-% in Wasser) über die Sprühwelle (1860 Umdrehungen pro min) eingedüst. Nach weiteren 30 s Mischzeit hatte sich ein feuchtes Granulat gebildet, das ausgetragen und anschließend in einem Wirbelschichttrockner 15 min lang getrocknet wurde. Die Zulufttemperatur lag bei 40 - 44°C, der Luftstrom betrug etwa 15 m3/min. Es resultierte ein Granulat mit einem Restwassergehalt von 0,8 Gew.-% (bestimmt durch Vakuumtrocknung bei 30 mbar, 45°C über 24 h). Die Siebanalyse zeigte 75 Gew.-% Gutkorn zwischen 0,4 und 1,6 mm, die ein Schüttgewicht von 870 g/I aufwiesen und als 0,5-prozentige Aufschlämmung in Wasser einen pH-Wert von 4,6 ergaben. Die Anteile unter 0,4 mm (10 Gew.-%) und über 1,6 mm (15 Gew.-%) wurden in diesem Versuch nicht zurückgeführt. Weitere Analysendaten enthält Tabelle 1.In a Patterson-Kelley V mixer with a content of 15 l, 2.03 kg of a moist filter cake (composition in percent by weight: diperoxydodecanedioic acid 29.6; sodium sulfate 54.8; dodecanedioic acid 2.6; water 13), 3.95 kg anhydrous sodium sulfate and 0.34 kg of magnesium sulfate (water content 30 wt .-%) submitted and for 1 min at 20 revolutions per min. premixed. Thereafter, 0.66 kg of a dispersion of a crotonic acid-vinyl acetate copolymer (molar ratio 1: 17.6; 16% by weight in water) was introduced into the rotating mixing container over a period of 3 minutes via the spray shaft (1860 revolutions per minute) injected. After a further 30 s of mixing time, moist granules had formed which were discharged and then dried in a fluidized bed dryer for 15 minutes. The supply air temperature was 40 - 44 ° C, the air flow was about 15 m 3 / min. The result was granules with a residual water content of 0.8% by weight (determined by vacuum drying at 30 mbar, 45 ° C. over 24 h). The sieve analysis showed 75% by weight of good grain between 0.4 and 1.6 mm, which had a bulk density of 870 g / l and gave a pH value of 4.6 as a 0.5% slurry in water. The proportions below 0.4 mm (10% by weight) and above 1.6 mm (15% by weight) were not returned in this experiment. Table 1 contains further analysis data.

Beispiel 2Example 2 Granulat mit Diperoxydodecan-1,12-disäureGranules with diperoxydodecane-1,12-diacid

Im selben Mischer wie in Beispiel 1 wurden 0,69 kg einer phlegmatisierten trockenen Diperdodecandisäure (Gehalt in Gew.-%: Persäure 34; Na2S04 63; Dodecandisäure 3), 1,08 kg trockenes NazS04, 0,23 kg MgSO4· H20 (Wassergehalt 30 Gew.-%) und 33 g pulvrige Polyacrylsäure (Molekulargewicht ca. 1000) vorgelegt und bei 20 Upm in 2 min lang vorgemischt. Über die Sprühwelle wurden dann innerhalb von 1 min 0,325 kg Wasser eingedüst. Das entstandene Feuchtgranulat wurde 30 min in der Wirbelschicht (Luftstrom ca. 2 m3/min, 40- C) getrocknet. Analysedaten siehe Tabelle 1.In the same mixer as in Example 1 were 0.69 kg of a dry desensitized diperdodecanedioic acid (content in wt .-% peracid 34; Na 2 S0 4 63; dodecanedioic 3), 1.08 kg of dry Na z S0 4, 0.23 kg of MgSO 4 .H 2 0 (water content 30% by weight) and 33 g of powdery polyacrylic acid (molecular weight approx. 1000) are introduced and premixed at 20 rpm in 2 minutes. 0.325 kg of water were then injected via the spray wave within 1 min. The resulting wet granules were dried in the fluidized bed for 30 minutes (air flow approx. 2 m 3 / min, 40 ° C.). For analysis data see table 1.

Beispiel 3Example 3 Granulat mit DiperoxybrassylsäureGranules with diperoxybrassylic acid

Im selben Mischer wie in Beispiel 1 wurden 1,685 kg einer trockenen phlegmatisierten Diperoxybrassylsäure (Gehalt in Gew.-%: Persäure 26,7; Na2S04 70,8; Brassylsäure 2,5), 2,56 kg wasserfreies Na2S04 und 0,26 kg MgSO4·H2O (Wassergehalt 30 %) während 3 min bei ca. 20 Upm in vermischt. Über die Sprühwelle wurden dann in einem Zeitraum von 0,5 min 0,42 kg einer Lösung von Polyacrylsäure (19 Gew.-% in H20) eingedüst. Nach einer Nachmischzeit von 1,5 min war ein Feuchtgranulat entstanden, das anschließend 20 min in einer Wirbelschichtanlage (7 m3 Luft pro min, 40°C) auf einen Wassergehalt von 1 Gew.-% getrocknet wurde. Laut Siebanalyse lagen 86,5 Gew.-% des Granulates zwischen 0,4 und 1,6 mm, 3,5 Gew.-% unter 0,4 mm und 10 Gew.-% über 1,6 mm. Das Schüttgewicht der Hauptfraktion betrug 810 g/l. Weitere Daten siehe Tabelle 1.In the same mixer as in Example 1, 1.655 kg of dry desensitized diperoxybrassylic acid (content in% by weight: peracid 26.7; Na 2 SO 4 70.8; brassylic acid 2.5), 2.56 kg of anhydrous Na 2 SO 4 and 0.26 kg of MgSO 4 .H 2 O (water content 30%) for 3 min at about 20 rpm. The spray wave was then used to inject 0.42 kg of a solution of polyacrylic acid (19% by weight in H 2 O) over a period of 0.5 min. After a post-mixing time of 1.5 minutes, moist granules had formed, which were then dried for 20 minutes in a fluidized bed system (7 m 3 of air per minute, 40 ° C.) to a water content of 1% by weight. According to sieve analysis, 86.5% by weight of the granules were between 0.4 and 1.6 mm, 3.5% by weight below 0.4 mm and 10% by weight above 1.6 mm. The bulk density of the main fraction was 810 g / l. For further data see table 1.

Beispiele 4 - 7Examples 4-7 Weitere Beispiele für Granulate mit Diperoxydodecan-1,12-disäureFurther examples of granules with diperoxydodecane-1,12-diacid

In äquivalenten Mischgranulationsapparaturen wie den Beispielen 1 und 2 wurden, ausgehend von feuchtem Persäure/Na2S04-Gemisch, Granulierhilfsmitteln und gegebenenfalls Tensiden sowie Phosphonsäuren verschiedene Feuchtgranulate hergestellt, die dann im Wirbelschichtverfahren nachgetrocknet wurden. Die Zusammensetzung gibt Tabelle 1 wieder.

Figure imgb0001
In equivalent mixing granulation apparatuses such as Examples 1 and 2, starting from a moist peracid / Na 2 S0 4 mixture, granulating aids and optionally surfactants and phosphonic acids, various moist granules were produced, which were then dried in a fluidized bed process. The composition is shown in Table 1.
Figure imgb0001

Beispiel 8Example 8 Bestimmung der LagerstabilitätDetermination of storage stability

Je 400 g der Granulate wurden in unkaschierte Waschmittelkartons der Größe E2 eingewogen und in diesen Behältern in einem Klimaraum bei 30° C und 80 % relativer Luftfeuchtigkeit gelagert. Zu Beginn und nach 4, 8, 12 und 16 Wochen Lagerzeit wurde der Gehalt an Aktivsauerstoff jodometrisch bestimmt. Aus den Ergebnissen dieser Untersuchungen, die in Tabelle 2 aufgeführt sind, geht die ausgezeichnete Lagerstabilität der Granulate hervor.

Figure imgb0002
400 g each of the granules were weighed into unclad detergent boxes of size E2 and stored in these containers in a climate room at 30 ° C and 80% relative humidity. At the beginning and after 4, 8, 12 and 16 weeks of storage, the content of active oxygen was determined iodometrically. The results of these investigations, which are listed in Table 2, show the excellent storage stability of the granules.
Figure imgb0002

Beispiel 9Example 9 Bestimmung der BleichaktivitätDetermination of bleaching activity

Die Bleichversuche wurden in Haushalts-Trommelwaschmaschinen bei einer Flottentemperatur von maximal 30°C und einer Waschzeit von 15 min durchgeführt, so daß sich Unterschiede im Löseverhalten der Granulate besonders deutlich zu erkennen gaben. Die Waschlauge (20 I pro Maschine) enthielt 120 g eines Waschmittels der folgenden Zusammensetzung:

Figure imgb0003
The bleaching tests were carried out in household drum washing machines at a liquor temperature of at most 30 ° C. and a washing time of 15 minutes, so that differences in the dissolving behavior of the granules were particularly evident. The wash liquor (20 l per machine) contained 120 g of a detergent of the following composition:
Figure imgb0003

Zusammen mit dem Waschmittel wurde soviel des jeweiligen Persäuregranulates dosiert, daß die Lauge 30 ppm Aktivsauerstoff enthielt. Zum Vergleich dienten Versuche mit nicht granulierter Diperoxydodecan-1,12- disäure, die in Pulverform 34 %-ig im Gemisch mit Na2S04 vorlag. Die Waschmaschinen enthielten jeweils 3,5 kg weißes Füllgewebe und je 2 Teststreifen mehrerer künstlicher Anschmutzungen, die zusammen gewaschen, 5 mal mit je 25 I Wasser gespült und im Tumbler getrocknet wurden. Zur Ermittlung der Bleichwirkung wurde dann die Lichtremission der Teststreifen bei 460 nm mit Hilfe eines Photometers Elrepho der Firma Zeiss gemessen.So much of the respective peracid granulate was metered in together with the detergent that the alkali contained 30 ppm of active oxygen. For comparison, experiments were carried out with non-granulated diperoxydodecane-1,12-diacid, which was in powder form 34% in a mixture with Na 2 SO 4 . The washing machines each contained 3.5 kg of white filler fabric and 2 test strips of several artificial stains, which were washed together, rinsed 5 times with 25 l of water and dried in a tumbler. To determine the bleaching effect, the light emission of the test strips at 460 nm was then measured using an Elrepho photometer from Zeiss.

Der Vergleich der Ergebnisse, die in Tabelle 3 für die unterschiedlichen Granulate, für nicht granulierte Persäure und für die bleichfreie Wäsche aufgeführt sind, läßt erkennen, daß die Granulate die Persäure auch unter den gewählten milden Bedingungen außerordentlich schnell in Freiheit setzen. Die Verschlechterung der Bleichwirkung gegenüber der nicht granulierten Persäure ist für die Praxis unbedeutend.

Figure imgb0004
A comparison of the results, which are shown in Table 3 for the different granules, for non-granulated peracid and for bleach-free washing, shows that the granules release the peracid extremely quickly, even under the mild conditions chosen. The worsening of the bleaching effect compared to the non-granulated peracid is insignificant in practice.
Figure imgb0004

Claims (11)

1. A bleaching agent in the form of a granulate of uniform composition which contains an aliphatic C4-C36 peroxycarboxylic acid solid at room temperature and hydratable inorganic salt, characterized in that it contains
3 to 50 % by weight of the peroxycarboxylic acid,
40 to 95 % by weight, based on the anhydrous form, of hydratable inorganic salt and
0.2 to 10 % by weight of an organic polymer compound soluble in alkaline-aqueous medium as granulation aid,
the granulate being free from microcrystalline cellulose where microfine starch is present, all the components are uniformly distributed in the individual grains of the granulate and the granulates alone, 0.5 % in water, have a pH value in the range from 3 to 7.
2. A bleaching agent in the form of a granulate of uniform composition which contains an aliphatic C4-Cg6 peroxycarboxylic acid solid at room temperature and hydratable inorganic salt, characterized in that it contains
3 to 50 % by weight of the peroxycarboxylic acid,
40 to 95 % by weight, based on the anhydrous form, of hydratable inorganic salt and
0.2 to 10 % by weight polyacrylic acid, maleic acid/acrylic acid copolymers (molar ratio 1 : 5 to 5 : 1) or crotonic acid/vinyl acetate copolymers (molar ratio 1 : 10 to 1 : 80) as granulation aid,
all the components are uniformly distributed in the individual grains of the granulate and the granulates alone, 0.5 % in water, have a pH value in the range from 3 to 7.
3. A bleaching agent as claimed in claim 1 or 2, characterized in that it contains sodium sulfate and magnesium sulfate in a ratio of 2 : 1 to 40 : 1, based on the anhydrous forms, as the hydratable inorganic salts.
4. A bleaching agent as claimed in any of claims 1 to 3, characterized in that it additionally contains a polyphosphonic acid.
5. A bleaching agent as claimed in any of claims 1 to 4, characterized in that it additionally contains an ether sulfate or alcohol sulfate as surfactant.
6. A bleaching agent as claimed in any of claims 1 to 5, characterized in that it contains a C10-C18 monoperoxycarboxylic acid or C6-C22 diperoxycarboxylic acid as the peroxycarboxylic acid and, in addition, from 0 to 2 % by weight of chelate complexing agents for heavy metals,
from 0 to 10 % by weight of alcohol sulfate or ether sulfate and
from 0 to 20 % by weight of water.
7. A bleaching agent as claimed in any of claims 1 to 6 containing
from 5 to 30 % by weight of C9-C13 a,m-diperoxydicarboxylic acid,
from 70 to 92 % by weight of a mixture of Na2S04 and MgS04 in a ratio of 2 : 1 to 40 : 1, based on the anhydrous forms,
from 0.5 to 4 % by weight of granulation aids from the group comprising polyacrylic acid, maleic acid - acrylic acid copolymers (molar ratio 0 : 5 to 5 : 1) and crotonic acid - vinyl acetate copolymers (molar ratio 1 : 10 to 1 : 80)
from 0.1 to 1 % by weight of polyphosphonic acid,
from 1 to 5 % by weight of fatty alcohol sulfate or fatty alcohol ether sulfate and
from 0.5 to 5 % by weight of water.
8. A process for producing the bleaching agent claimed in any of claims 1 to 7 in which the constituents are formed into granules by build-up granulation.
9. The use of the bleaching agent claimed in any of Claims 1 to 7 for oxidation, bleaching or disinfection.
10. The use claimed in claim 9 for bleaching fibers for fabrics.
11. The use claimed in claim 9 or 10 together with detergents.
EP86105669A 1985-05-02 1986-04-24 Bleaching agent, its preparation and its use Expired EP0200163B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86105669T ATE46916T1 (en) 1985-05-02 1986-04-24 BLEACHING INGREDIENT, ITS PRODUCTION AND USE.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3515712 1985-05-02
DE19853515712 DE3515712A1 (en) 1985-05-02 1985-05-02 FLEACH, ITS PRODUCTION AND USE

Publications (3)

Publication Number Publication Date
EP0200163A2 EP0200163A2 (en) 1986-11-05
EP0200163A3 EP0200163A3 (en) 1987-09-16
EP0200163B1 true EP0200163B1 (en) 1989-10-04

Family

ID=6269591

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86105669A Expired EP0200163B1 (en) 1985-05-02 1986-04-24 Bleaching agent, its preparation and its use

Country Status (6)

Country Link
US (1) US5091106A (en)
EP (1) EP0200163B1 (en)
JP (1) JPS61258072A (en)
AT (1) ATE46916T1 (en)
DE (2) DE3515712A1 (en)
ES (1) ES8704566A1 (en)

Families Citing this family (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5167854A (en) * 1985-08-21 1992-12-01 The Clorox Company Encapsulated enzyme in dry bleach composition
US5254287A (en) * 1985-08-21 1993-10-19 The Clorox Company Encapsulated enzyme in dry bleach composition
US4863626A (en) * 1985-08-21 1989-09-05 The Clorox Company Encapsulated enzyme in dry bleach composition
DE3683882D1 (en) * 1985-08-21 1992-03-26 Clorox Co STABLE PERSAEUR BLENDER.
US5093021A (en) * 1985-08-21 1992-03-03 The Clorox Company Encapsulated enzyme in dry bleach composition
ES2001074A6 (en) * 1985-08-21 1988-04-16 Clorox Co Dry peracid based bleaching product.
GB8619953D0 (en) * 1986-08-15 1986-09-24 Unilever Plc Peroxyacid bleach composition
DE3644564A1 (en) * 1986-12-27 1988-07-07 Henkel Kgaa METHOD FOR THE PRODUCTION OF GIANT, STABLE PERSAEURE CONCENTRATES BY COMPACTING GRANULATION
GB8810630D0 (en) * 1988-05-05 1988-06-08 Unilever Plc Process for preparing bodies containing peroxyacid & compositions comprising said bodies
US5358654A (en) * 1988-06-22 1994-10-25 Akzo Nobel N.V. Stable pourable aqueous bleaching compositions comprising solid organic peroxy acids and at least two polymers
US5126066A (en) * 1988-06-22 1992-06-30 Akzo N.V. Stable, pourable aqueous bleaching compositions comprising solid organic peroxy acids and at least two polymers
ES2055008T3 (en) * 1988-06-22 1994-08-16 Akzo Nv STABLE AND VERTIBLE AQUEOUS WHITENING COMPOSITIONS INCLUDING SOLID ORGANIC PEROXIACIDS AND AT LEAST TWO POLYMERS.
DE3822798A1 (en) * 1988-07-06 1990-01-11 Huels Chemische Werke Ag METHOD FOR THE PRODUCTION OF PHLEGMATIZED ALIPHATIC DIPEROXIDICARBONE ACIDS
US4917811A (en) * 1988-09-20 1990-04-17 Lever Brothers Company Bleach compositions and process for making same
US5049298A (en) * 1988-11-25 1991-09-17 Akzo Nv Process for the preparation of bleaching granules
US5296156A (en) * 1988-11-25 1994-03-22 Akzo N.V. Bleaching granules
CA2015490A1 (en) * 1989-05-01 1990-11-01 Charles E. Kellner Agglomerated peroxyacid bleach granule and process for making same
GB8922179D0 (en) * 1989-10-02 1989-11-15 Rohm & Haas Polymer-containing granulates
US5279757A (en) * 1990-04-06 1994-01-18 Hoechst Aktiengesellschaft Stable peroxycarboxylic acid granule comprising an imidoperoxycarboxylic acid or salt thereof
US5055218A (en) * 1990-04-13 1991-10-08 The Procter & Gamble Company Bleach granules containing an amidoperoxyacid
DE4012769A1 (en) * 1990-04-21 1991-10-24 Hoechst Ag STABLE PEROXICARBONIC ACID GRANULES
TR25837A (en) * 1990-05-31 1993-09-01 Procter & Gamble  METHOD OF POWDERED PEROXIACID DEGREASER GRANULATED AND FOR THIS.
GB9016504D0 (en) * 1990-07-27 1990-09-12 Warwick Int Ltd Granular bleach activator compositions
JP3231834B2 (en) * 1991-05-04 2001-11-26 クラリアント・ゲゼルシヤフト・ミト・ベシユレンクテル・ハフツング Imidocarboxylic acid activator and sulfimide carboxylic acid activator, methods for their preparation and their use
US5234617A (en) * 1992-04-20 1993-08-10 Kathleen B. Hunter Aqueous liquid bleach compositions with fluorescent whitening agent and polyvinyl pyrrolidone or polyvinyl alcohol
EP0592033A1 (en) * 1992-10-07 1994-04-13 The Procter & Gamble Company Process for making peroxyacid containing particles
US5409632A (en) * 1992-11-16 1995-04-25 The Procter & Gamble Company Cleaning and bleaching composition with amidoperoxyacid
US5932532A (en) * 1993-10-14 1999-08-03 Procter & Gamble Company Bleach compositions comprising protease enzyme
WO1996009983A1 (en) * 1994-09-26 1996-04-04 Fmc Corporation Stable peracid sols, gels and solids and a process therefor
US6017865A (en) * 1995-12-06 2000-01-25 The Procter & Gamble Company Perfume laundry detergent compositions which comprise a hydrophobic bleaching system
WO1997033957A1 (en) * 1996-03-15 1997-09-18 Amway Corporation Powder detergent composition having improved solubility
US5714451A (en) * 1996-03-15 1998-02-03 Amway Corporation Powder detergent composition and method of making
US5714450A (en) * 1996-03-15 1998-02-03 Amway Corporation Detergent composition containing discrete whitening agent particles
WO1997033958A1 (en) * 1996-03-15 1997-09-18 Amway Corporation Discrete whitening agent particles, method of making, and powder detergent containing same
US6177397B1 (en) 1997-03-10 2001-01-23 Amway Corporation Free-flowing agglomerated nonionic surfactant detergent composition and process for making same
GB2345701A (en) * 1999-01-12 2000-07-19 Procter & Gamble Particulate bleaching components
AU5753000A (en) 1999-06-21 2001-01-09 Procter & Gamble Company, The Detergent composition
DE10361100A1 (en) * 2003-06-13 2005-01-05 Henkel Kgaa Storage-stable capsules based on peroxycarboxylic acids
US8034759B2 (en) 2008-10-31 2011-10-11 Ecolab Usa Inc. Enhanced stability peracid compositions
GB201402257D0 (en) 2014-02-10 2014-03-26 Revolymer Ltd Novel Peracid - containing particle

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3664961A (en) * 1970-03-31 1972-05-23 Procter & Gamble Enzyme detergent composition containing coagglomerated perborate bleaching agent
LU70331A1 (en) * 1974-06-17 1976-05-31
GB1456591A (en) * 1973-05-14 1976-11-24 Procter & Gamble Stable bleaching compositions
GB1476682A (en) * 1973-05-16 1977-06-16 Ppg Industries Inc Bleaching formulation
US4126573A (en) * 1976-08-27 1978-11-21 The Procter & Gamble Company Peroxyacid bleach compositions having increased solubility
US4497757A (en) * 1983-01-31 1985-02-05 The Procter & Gamble Company Energy efficient hydration process
JPS6060905A (en) * 1983-09-08 1985-04-08 Nippon Peroxide Co Ltd Manufacture of peroxide having superior disintegrability in water

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA651777A (en) * 1962-11-06 C. M. Van Embden Ian Bleaching compositions
DE1240508B (en) * 1963-04-01 1967-05-18 Degussa Process for granulating perborate
US3770816A (en) * 1969-07-23 1973-11-06 Ppg Industries Inc Diperisophthalic acid compositions
US3639285A (en) * 1969-07-23 1972-02-01 Ppg Industries Inc Novel bleaching compositions and use thereof
GB1387167A (en) * 1972-09-28 1975-03-12 Procter & Gamble Ltd Bleaching agent
CA1029153A (en) * 1973-05-14 1978-04-11 Thomas W. Gougeon Bleaching composition and methods
DE2413561A1 (en) * 1974-03-21 1975-10-02 Henkel & Cie Gmbh STORAGE-RESISTANT, EASILY-RELEASE DETERGENT ADDITIVE AND METHOD FOR MANUFACTURING IT
GB1534261A (en) * 1974-11-08 1978-11-29 Reckitt & Colmann Prod Ltd Cleaning composition
US4013581A (en) * 1975-07-10 1977-03-22 The Procter & Gamble Company Bleach tablet composition
GB1569258A (en) * 1975-11-18 1980-06-11 Interox Chemicals Ltd Bleaching compositions and processes
GB1568358A (en) * 1975-11-18 1980-05-29 Interox Chemicals Ltd Aromatic peroxyacids and their use in bleaching processes
DE2622463C3 (en) * 1976-05-20 1985-06-05 Basf Ag, 6700 Ludwigshafen Process for the purification of copolymers containing crotonic acid
US4170453A (en) * 1977-06-03 1979-10-09 The Procter & Gamble Company Peroxyacid bleach composition
US4287135A (en) * 1978-10-25 1981-09-01 Reinhard Stober Stabilized diperoxyalkanedioic acids and aromatic peroxycarboxylic acids
EP0027693B2 (en) * 1979-10-18 1988-05-11 Interox Chemicals Limited Magnesium salts of peroxycarboxylic acids, processes for their preparation and their use as bleaching agents in washing compositions, and processes
US4259201A (en) * 1979-11-09 1981-03-31 The Procter & Gamble Company Detergent composition containing organic peracids buffered for optimum performance
DE3266563D1 (en) * 1981-09-08 1985-10-31 Interox Chemicals Ltd Granulation
DE3305637A1 (en) * 1983-02-18 1984-08-23 Basf Ag, 6700 Ludwigshafen COPOLYMERISATE, THEIR PRODUCTION AND THEIR USE AS AUXILIARIES IN DETERGENT AND CLEANING AGENTS
GB8332682D0 (en) * 1983-12-07 1984-01-11 Procter & Gamble Laundry additive products
DE3683882D1 (en) * 1985-08-21 1992-03-26 Clorox Co STABLE PERSAEUR BLENDER.

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3664961A (en) * 1970-03-31 1972-05-23 Procter & Gamble Enzyme detergent composition containing coagglomerated perborate bleaching agent
GB1456591A (en) * 1973-05-14 1976-11-24 Procter & Gamble Stable bleaching compositions
GB1476682A (en) * 1973-05-16 1977-06-16 Ppg Industries Inc Bleaching formulation
LU70331A1 (en) * 1974-06-17 1976-05-31
US4126573A (en) * 1976-08-27 1978-11-21 The Procter & Gamble Company Peroxyacid bleach compositions having increased solubility
US4497757A (en) * 1983-01-31 1985-02-05 The Procter & Gamble Company Energy efficient hydration process
JPS6060905A (en) * 1983-09-08 1985-04-08 Nippon Peroxide Co Ltd Manufacture of peroxide having superior disintegrability in water

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Encyclopedia of Polymer Science and Technology, Vol.3, pages 285-290 *
Ullmanns Encyklopädie der technischen Chemie, 4. Aufl., Band 22, Seiten 171-172 *

Also Published As

Publication number Publication date
ATE46916T1 (en) 1989-10-15
JPS61258072A (en) 1986-11-15
EP0200163A3 (en) 1987-09-16
ES554586A0 (en) 1987-04-01
EP0200163A2 (en) 1986-11-05
US5091106A (en) 1992-02-25
DE3515712A1 (en) 1986-11-06
ES8704566A1 (en) 1987-04-01
DE3666048D1 (en) 1989-11-09

Similar Documents

Publication Publication Date Title
EP0200163B1 (en) Bleaching agent, its preparation and its use
DE2338412C2 (en) Bleaching aid suitable for use in detergents and bleaching agents and a process for its production
DE2820990C2 (en)
EP1475350B1 (en) Coated sodium percarbonate granules with improved storage stability
DE2138584C3 (en) Shelf-life bleach suitable for use in detergents and process for making same
EP0170791A1 (en) Process for the production of a washing additive in the form of tablets
DE2655971A1 (en) STABILIZED, ACTIVATED BLEACHING COMPOSITION
DE2737864A1 (en) PARTICLES FROM A PEROXIC ACID BLEACHING AGENT, PROCESS FOR THEIR MANUFACTURING AND THIS BLEACHING COMPOSITION
DE2446619C2 (en)
DE19641708A1 (en) Process for the preparation of a coated bleach activator granulate
AT394380B (en) PARTICULATE AND SOFTENING COARSE DETERGENT FOR TEXTILES, METHOD FOR THE PRODUCTION THEREOF, AGGLOMERED BENTONITE PARTICLES FOR THE DETERGENT AND METHOD FOR THEIR PRODUCTION
EP0272402B1 (en) Process for coating granules of peroxycarboxylic acids
EP0868396B1 (en) Solid peroxo compounds and peroxy compounds stabilised by coating
DE2857472A1 (en) DETERGENT TABLET WITH A HYDRATED SALT COVER AND METHOD FOR PRODUCING THE TABLET
EP0013028A1 (en) Detergent with a polydimethyl-siloxane content possessing an anti-foaming activity, and process for its production
DE602005004607T2 (en) METHOD FOR PRODUCING GRANULATE COMPOSITIONS
EP0985728B1 (en) Bleach activator granulate
CH643590A5 (en) PARTICULATE BLENDER.
DE1469279B2 (en) Yellowing-inhibiting detergent additives and detergents containing these additives
DE2539110B2 (en) Process for washing or bleaching textiles, and means for carrying out the process
DE4040654A1 (en) GRANULES WITH COVERED BLEACH ACTIVATOR
EP0623593A2 (en) Process for neutralising the acid form of anionic surfactant, agglomerates and detergent thereby obtained
DE2113732A1 (en) Anti-microbial washing composns - contg terpenes as bactericides and optical brighteners
EP0079105B1 (en) Foam-controlled washing agents
DE2420762A1 (en) PROCESS FOR IMPROVING THE STABILITY OF SODIUM PERCARBONATE IN BLEACHING AND DETERGENT DETERGENTS

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE FR GB IT LI NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE FR GB IT LI NL SE

17P Request for examination filed

Effective date: 19880229

17Q First examination report despatched

Effective date: 19880829

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE FR GB IT LI NL SE

REF Corresponds to:

Ref document number: 46916

Country of ref document: AT

Date of ref document: 19891015

Kind code of ref document: T

ET Fr: translation filed
REF Corresponds to:

Ref document number: 3666048

Country of ref document: DE

Date of ref document: 19891109

ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: UNILEVER N.V.

Effective date: 19900704

NLR1 Nl: opposition has been filed with the epo

Opponent name: UNILEVER N.V.

ITTA It: last paid annual fee
PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19920416

Year of fee payment: 7

R26 Opposition filed (corrected)

Opponent name: UNILEVER N.V.

Effective date: 19900704

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19930324

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19930327

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19930408

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19930414

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19930419

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19930425

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19930430

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19930608

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19940424

Ref country code: AT

Effective date: 19940424

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19940430

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19940430

Ref country code: BE

Effective date: 19940430

BERE Be: lapsed

Owner name: HENKEL K.G.A.A.

Effective date: 19940430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19941101

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19940424

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19941229

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19950103

EUG Se: european patent has lapsed

Ref document number: 86105669.5

Effective date: 19931110

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

27W Patent revoked

Effective date: 19950213

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO