EP0088866A1 - Aqueous stable suspensions of water-insoluble silicates capable of binding calciumions, and their use in the production of washing and cleaning agents - Google Patents

Aqueous stable suspensions of water-insoluble silicates capable of binding calciumions, and their use in the production of washing and cleaning agents Download PDF

Info

Publication number
EP0088866A1
EP0088866A1 EP83100470A EP83100470A EP0088866A1 EP 0088866 A1 EP0088866 A1 EP 0088866A1 EP 83100470 A EP83100470 A EP 83100470A EP 83100470 A EP83100470 A EP 83100470A EP 0088866 A1 EP0088866 A1 EP 0088866A1
Authority
EP
European Patent Office
Prior art keywords
water
suspension
component
formula
binding
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.)
Granted
Application number
EP83100470A
Other languages
German (de)
French (fr)
Other versions
EP0088866B1 (en
Inventor
Manfred Dr. Diehl
Roland Bergmann
Günter Stadtmüller
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.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
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 Degussa GmbH filed Critical Degussa GmbH
Priority to AT83100470T priority Critical patent/ATE20537T1/en
Publication of EP0088866A1 publication Critical patent/EP0088866A1/en
Application granted granted Critical
Publication of EP0088866B1 publication Critical patent/EP0088866B1/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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C11D3/1286—Stabilised aqueous aluminosilicate suspensions

Definitions

  • Sodium is preferred as the cation, but it can also be replaced by lithium, potassium, ammonium or magnesium.
  • miniumsilikate A lu- capable of binding calcium compounds are hereinafter simply referred to "miniumsilikate A lu-" as. This applies in particular to the sodium aluminum silicates to be used with preference; all statements made for their use according to the invention and all statements regarding their production and properties apply accordingly to the entirety of all the compounds defined above.
  • the aluminum silicates which are particularly suitable for use in detergents and cleaning agents have a calcium binding capacity of preferably 50 to 200 mg CaO / g of the anhydrous aluminum silicate. If reference is made to anhydrous aluminum silicate in the following, it means the state of the aluminum silicate which is reached after drying for one hour at 800 ° C. During this drying, the adhering and bound water is practically completely removed.
  • the aluminum silicates are supplied or used, for example, as an aqueous suspension. This would involve certain improvements in the suspension properties - e.g. the suspension stability and the pumpability - the aluminum silicates dispersed in the aqueous phase are still desirable.
  • R an aliphatic radical with 1 to 15, for example -CH 3 , -C 2 H 5 , propyl, butyl, pentyl, hexyl, heptyl, octyl and nonyl, preferably with 9 carbon atoms such as nonyl be.
  • the radical R can be substituted in the ortho, meta and / or para position. It is also possible to use mixtures in which, in addition to p-substituted aryl rings, o-substituted benzene rings are also present. Mixtures are preferably used in which there is 90% p-substitution and 10% ortho-substitution.
  • n can mean 2 to 7, preferably 4 to 6, in particular 5 in the case of one alkylphenol ethoxylate used in the mixture and 8 to 15, preferably 8 to 12, in particular 9 or 10 in the other alkylphenol ethoxylate.
  • n can also mean 7 or 9 or 12 in the case of mixtures of the alkylphenolates.
  • component A can be crystalline.
  • y can be a number from 1.3 to 4.
  • crystalline component A can be a type A zeolite.
  • foam-suppressing additives i.e. Compounds that improve the solubility of the added dispersants in the aqueous phase.
  • solubilizers i.e. Compounds that improve the solubility of the added dispersants in the aqueous phase.
  • foam-suppressing substances for example foam-suppressing soap, silicone defoamers, foam-suppressing triazine derivatives, all of which are known and familiar to the expert, can be used as foam suppressors.
  • foam suppressors for example foam-suppressing soap, silicone defoamers, foam-suppressing triazine derivatives, all of which are known and familiar to the expert, can be used as foam suppressors.
  • foam suppressors can be used as foam suppressors.
  • foam suppressors for example foam-suppressing soap, silicone defoamers, foam-suppressing triazine derivatives, all of which are known and familiar to the expert, can be used as foam suppress
  • solubilizing substances is generally not necessary, but it may be appropriate if the suspension according to the invention contains a hydrophilic, but sparingly water-soluble colloid, such as polyvinyl alcohol, as a stabilizing agent. It is advantageous e.g. a solubilizer - dimethyl sulfoxide is very suitable - if the concentration of a stabilizing agent of group 1, which is only slightly soluble in water, is higher than about 1%.
  • the proportion of the solubilizer in the total suspension can, for example, be of the same order of magnitude as the proportion of the stabilizing agent.
  • Hydrotrophic agents such as, for example, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid or their water-soluble salts or also octyl sulfate are suitable.
  • the aluminum silicates of component A to be used can be amorphous or crystalline products, although mixtures of amorphous and crystalline products and also partially crystalline products can of course also be used.
  • the aluminum silicates can be naturally occurring or else synthetically produced products, the synthetically produced products being preferred.
  • the production can, for example: by reaction of water-soluble silicates with water-soluble aluminates in the presence of water.
  • aqueous solutions of the starting materials can be mixed with one another or a component present in the solid state can be reacted with the other component present as an aqueous solution.
  • the desired aluminum silicates are also obtained by mixing the two components present in the solid state in the presence of water.
  • Aluminum silicates can also be produced from A1 (OH) 2 , Al 2 O 3 or SiO 2 by reaction with alkali silicate or aluminate solutions. The production can also be carried out by other known processes. In particular relates the invention relates to aluminum silicates which have a three-dimensional space lattice structure.
  • the preferred calcium binding capacity which is approximately in the range from 100 to 200 mg CaO / g AS, usually around 100 to 180 mg CaO / g AS, is found above all in compounds of the composition:
  • This empirical formula comprises two types of different crystal structures (or their non-crystalline precursors), which also differ in their empirical formulas.
  • the amorphous or crystalline aluminum silicate present in aqueous suspension can be separated from the remaining aqueous solution by filtration and at temperatures of e.g. Dry 50 to 400 ° C. Depending on the drying conditions, the product contains more or less bound water.
  • Such high drying temperatures are generally not recommended; Expediently, the temperature does not exceed 200 ° C. if the aluminum silicate is intended for use in detergents and cleaning agents.
  • the aluminum silicates do not need to be dried at all to prepare a suspension according to the invention will; rather - and this is particularly advantageous - an aluminum silicate that is still moist from manufacture can be used.
  • the particle size of the individual aluminum silicate particles can be different and e.g. are in the range between 0.1 ⁇ and 0.1 mm. This refers to the primary particle size, i.e. the size of the particles obtained during the precipitation and, if appropriate, the subsequent crystallization. It is particularly advantageous to use aluminum silicates which consist of at least 80% by weight of particles with a size of 10 to 0.01 ⁇ , in particular 8 to 0.1 g.
  • These aluminum silicates preferably no longer contain primary or secondary particles with diameters above 45.
  • Secondary particles are particles which are formed by agglomeration of the primary particles into larger structures.
  • the use of the aluminum silicates which are still moist from their preparation for the preparation of the suspensions according to the invention has proven particularly useful since it has been found that the formation of secondary particles is practically completely prevented when these still moist products are used .
  • powdered zeolite of type A with a particularly defined particle spectrum is used as component A.
  • Such zeolite powder can according to DE-AS 24 47 021, DE-AS 25 17 218, DE-OS 26 52 419, DE-OS 26 51 420, DE-OS 26 51 436 D E-OS 26 51 437, DE-OS 26 51 445, DE-OS 26 51 485 are produced. They then have the particle distribution curves given there.
  • a powdery zeolite of type A can be used, which has the particle size distribution described in DE-OS 26 51 485.
  • the concentration of component A can preferably be 44 to 55% by weight, in particular 46 to 52% by weight or more.
  • Component B can be a mixture of at least two alkylphenol ethoxylates of the formula be.
  • the phenol ring can be substituted both in the para and in the ortho position.
  • the alkylphenol ethoxylates can be used in any mixture, preferably in a ratio of 1: 9 to 9: 1, preferably 2: 3 to 3: 2, in particular 0.9: 1.1 to 1.1: 0.9.
  • the concentration of this mixture in the aqueous suspension can preferably be from 1 to 2% by weight, in particular 1.4 to 1.6% by weight. be. This concentration is sufficient to stabilize a suspension with a solids content of 50% by weight or more.
  • the suspension according to the invention has the advantage that it is stable to sedimentation in the temperature range from 10 to 50 ° C. and has a pumpable consistency.
  • a further advantage is that the alkylphenol ethoxylate is liquid at room temperature and therefore does not need to be heated.
  • the known suspension has a lower sedimentation stability and, with the same type of incorporation, is not homogeneous at room temperature and is therefore more difficult to process.
  • the aqueous suspensions can contain, in addition to the constituents A and B mentioned and, in addition to any starting materials for the production of these constituents, any remaining constituents, further constituents in comparatively small amounts. If the suspension is to be further processed into detergents and cleaning agents, the additional substances present are of course expediently substances which are suitable as constituents of detergents and cleaning agents.
  • an indication of the stability of the suspensions is provided by a simple test in which an aluminum silicate suspension of the desired concentration - for example 31% strength - is produced, which contains a dispersant according to the invention and optionally other substances, for example detergent constituents such as pentasodium triphosphate, in different amounts. The influence of the added substance can then be visually observed in the settling behavior of the suspension. After standing for 24 hours, a preferred suspension should generally be at most so far removed that the protruding clear or silicate-free solution does not make up more than 20%, preferably not more than 10%, in particular not more than 6% of the total height.
  • the amount of additives should be kept such that the suspension can still be pumped over again properly after 12 hours, preferably after 24 hours and in particular also after 48 hours in the storage container and pipe or hose lines.
  • the settling behavior of the suspension is checked at room temperature - with a total height of the suspension of 10 cm. They are also after 4. or Fully pumpable for 8 days. Also this information to the suspension stability only give A nhalts.; It depends on the individual case which suspension stability is to be set.
  • the suspension according to the invention When using the suspension according to the invention as a stock suspension to the longer L a delay in a reservoir from which it can be withdrawn by pumping as required, it may be desirable to keep the proportion of other components, for example, of detergents and cleaning agents is low or in this very to renounce.
  • the suspensions can be prepared by simply mixing their constituents, the aluminum silicates e.g. can be used as such or - if necessary from the production stage - already moist or in an aqueous suspension. It is particularly advantageous to use aluminum silicates that are still moist, e.g. stir into component B as a filter cake.
  • the suspensions according to the invention are distinguished by high stability and by further advantages. Their stabilizing effect is particularly in the case of aluminum silicates with particle sizes of 5 to 30 p. particularly valuable. They are pumpable so that they allow easy handling of moist aluminum silicates. The suspensions can be pumped around perfectly even after long interruptions in the pumping process. Because of their high stability, the suspensions can also be transported in conventional tank and tank wagons without fear of the formation of unusable or disruptive residues. This makes the suspensions ideal as a form of delivery of aluminum silicates for delivery to detergent manufacturers, for example.
  • the suspensions can be stored at room temperature or at higher temperatures, pumped through pipes or transported in some other way. Usually done the handling of the suspensions at temperatures between room temperature - usually preferred - and about 60 ° C.
  • the suspensions according to the invention are particularly suitable for further processing to appear dry, pourable or free-flowing products, for example for the production of powdered water softeners, e.g. by spray drying.
  • the suspensions are therefore of considerable importance in the production of powdered aluminum silicates. There are no annoying residues when feeding the aqueous suspensions to the drying apparatus. It has also been shown that the suspensions of the invention enable processing to extremely dust-free products.
  • suspensions according to the invention are already as such, i.e. usable without further processing with or without further washing, bleaching and / or cleaning additives, for example as water softening agents, washing or cleaning agents and in particular as liquid abrasives with increased suspension stability.
  • a particularly important use of the suspension is the further processing into dry-appearing, free-flowing or free-flowing detergents and cleaning agents which contain further compounds in addition to the suspension components.
  • the suspensions according to the invention are particularly suitable for the production of powder detergents.
  • an aqueous, flowable premix of the individual constituents of the agents is used and these are converted into a pourable product in the usual way.
  • the aluminum silicates defined above are used in the form of the suspension according to the invention.
  • the suspensions according to the invention can be processed into solid, pourable detergents and cleaning agents by any known method.
  • a suspension according to the invention - for example from a storage container - is mixed with at least one detergent, bleaching or cleaning component of the agent to be prepared, and the mixture is then mixed by any process converted into the powdered product.
  • a complexing agent is advantageously added, i.e. a compound that is able to complexly bind the alkaline earth metal ions responsible for water hardness, especially magnesium and calcium ions.
  • the suspension according to the invention is preferably combined with at least one water-soluble surfactant which does not belong to the possible components of component B.
  • the suspensions according to the invention can be used with substances capable of binding water of crystallization be combined, expediently by spraying the suspension onto the compounds which are present in a mixer and are capable of binding water of crystallization, so that a constant solid, dry-appearing product is obtained with constant mixing.
  • the suspensions according to the invention, mixed as a "slurry" are subjected to the atomization drying with at least one further washing, bleaching or cleaning compound.
  • Detergents which have been produced using the suspension described above can be composed in various ways. In general, they contain at least one water-soluble surfactant which does not belong to the dispersants used according to the invention and which are present in the claimed aluminum silicate suspensions. In general, in addition to at least one further compound which has a washing, bleaching or cleaning action and is inorganic or organic, they contain an aluminum silicate as defined above as a calcium-binding compound. In addition, other customary auxiliaries and additives, which are usually present in smaller amounts, can be present in such agents.
  • a Zeolit-A filter cake is mixed with water and stabilizer.
  • the zeolite A used is identical to that of Examples 1 to 25 above.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Paper (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Distillation Of Fermentation Liquor, Processing Of Alcohols, Vinegar And Beer (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

There are provided aqueous pumpable stable suspensions of a water insoluble silicate capable of binding calcium ions which contain based on the total weight of the aqueous suspension (A) as the silicate capable of binding calcium 0.5 to 80 weight percent of a finely divided, bound water containing, synthetically produced, water insoluble compound of the general formula (Cat2/nO)x.Me2O3.(SiO2)y (I), in which Cat is a cation exchangeable with calcium and which has the valence n, x is a number from 0.7 to 1.5, Me is boron or aluminum and y is a number between 0.8 and 6 and (B) as a dispersingly active component 0.5 to 6 weight percent of a mixture of at least two different alkylphenolethoxylates of the formula <IMAGE> (II) where R is an alkyl group of 1 to 15 carbon atoms. The component A especially can be a zeolite A while component B can consist of two alkylphenolethoxylates of formula (II) in which m is 2 to 7 and m is 8 to 15. The suspension can be employed for the production of powdery washing agents and detergents.

Description

Wässrige stabile Suspensionen wasserunlöslicher, zum Binden von Calciumionen befähigter Silikate und deren Verwendung zur Herstellung von Wasch- und Reinigungsmitteln.Aqueous stable suspensions of water-insoluble silicates capable of binding calcium ions and their use in the production of detergents and cleaning agents.

Es wurden bereits Verfahren zum Waschen und Reinigen von festen Materialien, insbesondere von Textilien, sowie für die Durchführung der Verfahren geeignete Wasch- und Reinigungsmittel vorgeschlagen, bei welchen die Rolle der Calcium komplex bindenden Phosphate ganz oder teilweise von zum Binden von Calcium befähigten, feinverteilten, im allgemeinen gebundenes Wasser enthaltenden, wasserunlöslichen Aluminiumsilikaten übernommen wird (vgl. DE-OS 24 12 837).Processes for washing and cleaning solid materials, in particular textiles, and detergents and cleaning agents suitable for carrying out the processes have already been proposed, in which the role of the calcium complex-binding phosphates wholly or partly of finely divided, capable of binding calcium, water-insoluble aluminum silicates containing generally bound water is taken over (cf. DE-OS 24 12 837).

Es handelt sich dabei um Verbindungen der allgemeinen Formel I

Figure imgb0001
in der Kat ein mit Calcium austauschbares Kation der Wertigkeit n, x eine Zahl von 0,7 bis 1,5, Me Aluminium und y eine Zahl von 0,8 bis 6, vorzugsweise von 1,3 bis 4, bedeuten.These are compounds of the general formula I.
Figure imgb0001
 in the cat a calcium-exchangeable cation of the valence n, x is a number from 0.7 to 1.5, Me aluminum and y is a number from 0.8 to 6, preferably from 1.3 to 4.

Als Kation kommt bevorzugt Natrium in Frage, es kann aber auch durch Lithium, Kalium, Ammonium oder Magnesium ersetzt sein.Sodium is preferred as the cation, but it can also be replaced by lithium, potassium, ammonium or magnesium.

Die oben definierten, zum Binden von Calcium befähigten Verbindungen werden im folgenden der Einfachheit halber als "Alu- miniumsilikate" bezeichnet. Dies gilt insbesondere auch für die bevorzugt zu verwendenden Natriumaluminiumsilikate; alle für deren erfindungsgemäße Verwendung gemachten Angaben und sämtliche Angaben über deren Herstellung und Eigenschaften gelten entsprechend für die Gesamtheit aller oben definierten Verbindungen.Defined above, capable of binding calcium compounds are hereinafter simply referred to "miniumsilikate A lu-" as. This applies in particular to the sodium aluminum silicates to be used with preference; all statements made for their use according to the invention and all statements regarding their production and properties apply accordingly to the entirety of all the compounds defined above.

Die für den Einsatz in Wasch- und Reinigungsmitteln besonders geeigneten Aluminiumsilikate besitzen ein Calciumbindevermögen von vorzugsweise 50 bis 200 mg CaO/g des wasserfreien Aluminiumsilikats. Wenn im folgenden auf wasserfreies Aluminiumsilikat Bezug genommen wird, so ist damit der Zustand der Aluminiumsilikate gemeint, der nach einstündigem Trocknen bei 800°C erreicht wird. Bei dieser Trocknung wird das anhaftende und das gebundene Wasser praktisch völlig entfernt.The aluminum silicates which are particularly suitable for use in detergents and cleaning agents have a calcium binding capacity of preferably 50 to 200 mg CaO / g of the anhydrous aluminum silicate. If reference is made to anhydrous aluminum silicate in the following, it means the state of the aluminum silicate which is reached after drying for one hour at 800 ° C. During this drying, the adhering and bound water is practically completely removed.

Bei der Herstellung von Wasch- oder Reinigungsmitteln, in denen neben üblichen Bestandteilen derartiger Mittel die oben definierten Aluminiumsilikate vorliegen, wird vorteilhaft von Aluminiumsilikaten ausgegangen, die feucht sind, beispielsweise noch von ihrer Herstellung her. Man vermischt dabei die feuchten Verbindungen wenigstens mit einem Teil der übrigen Bestandteile des herzustellenden Mittels und überführt das. Gemisch durch bekannte Maßnahmen, wie zum Beispiel Sprühtrocknen in das fertige Wasch- oder Reinigungsmittel als Endprodukt, beispielsweise in ein schüttfähiges Produkt.In the production of detergents or cleaning agents in which the aluminum silicates defined above are present in addition to the usual constituents of such agents, aluminum silicates which are moist, for example still from their production, are advantageously used. The moist compounds are mixed with at least some of the remaining constituents of the agent to be prepared and the mixture is transferred by known measures, such as spray drying, into the finished washing or cleaning agent as the end product, for example into a pourable product.

Im Rahmen des vorstehend skizzierten Herstellungsverfahrens für Wasch- oder Reinigungsmittel werden die Aluminiumsilikate beispielsweise als wässrige Suspension angeliefert bzw. eingesetzt. Dabei wären gewisse Verbesserungen der Suspensionseigenschaften - z.B. der Suspensionsstabilität und der Pumpbarkeit - der in wässriger Phase dispergierten Aluminiumsilikate noch erwünscht.As part of the manufacturing process for detergents or cleaning agents outlined above, the aluminum silicates are supplied or used, for example, as an aqueous suspension. This would involve certain improvements in the suspension properties - e.g. the suspension stability and the pumpability - the aluminum silicates dispersed in the aqueous phase are still desirable.

Es ist bekannt zur Bildung von Aluminiumsilikatsuspensionen Alkylphenoläthylenaddukte zu verwenden. Bevorzugterweise werden Addukte mit 6 bis 7 Mol Äthylenoxid verwendet (DE-OS 26 15 698).It is known to use alkyl phenol ethylene adducts to form aluminum silicate suspensions. Adducts with 6 to 7 moles of ethylene oxide are preferably used (DE-OS 26 15 698).

Es wurde nun gefunden, daß bestimmte Mischungen von Alkylphenoläthoxylaten in ganz besonderem Maße die Fähigkeit besitzen, Suspensionen der obigen Calcium bindenden Aluminiumsilikate derart zu stabilisieren, daß diese selbst bei hohem Feststoffgehalt lange Zeit stabil und auch nach langem Stehen noch einwandfrei pumpbar sind. überraschenderweise hat sich gezeigt, daß diese bestimmten Mischungen in der Lage sind, sogar feuchte Aluminiumsilikate, die einen Wassergehalt von 70 % und weniger aufweisen, über längere Zeit ohne Rühren sedimentationsstabil zu halten.It has now been found that certain mixtures of alkylphenol ethoxylates have a very particular ability to stabilize suspensions of the above calcium-binding aluminum silicates in such a way that they are stable for a long time even at a high solids content and can still be pumped perfectly even after standing for a long time. Surprisingly, it has been shown that these certain mixtures are capable of keeping even moist aluminum silicates, which have a water content of 70% and less, sedimentation-stable over a long period of time without stirring.

Gegenstand der Erfindung ist eine wässrige, pumpfähige, stabile Suspension eines wasserunlöslichen, zum Binden von Calciumionen befähigten Silikates, welches dadurch gekennzeichnet ist, daß sie, bezogen auf das Gesamtgewicht der wässrigen Suspension

  • A) als zum Binden von Calcium befähigtes Silikat 0,5 bis 80 Gewichtsprozent einer feinverteilten, gebundenes Wasser enthaltenden, synthetisch hergestellten, wasserunlöslichen Verbindung der allgemeinen Formel
    Figure imgb0002
    in der Kat ein mit Calcium austauschbares Kation der Wertigkeit n, x eine Zahl von 0,7 bis 1,5, Me Bor oder Aluminium und y eine Zahl von 0,8 bis 6 bedeuten, und
  • B) als dispergierend wirkenden Bestandteil 0,5 bis 6 Gewichtsprozent, vorzugsweise 1 bis 2 Gew.-%, insbesondere 1,4 bis 1,6 Gew.-% eine Mischung von mindestens zwei verschiedenen Alkylphenoläthoxylaten der Formel
    Figure imgb0003
    enthält.
The invention relates to an aqueous, pumpable, stable suspension of a water-insoluble silicate capable of binding calcium ions, which is characterized in that it is based on the total weight of the aqueous suspension
  • A) as silicate capable of binding calcium 0.5 to 80 percent by weight of a finely divided, bound water containing, synthetically produced, water-insoluble compound of the general formula
    Figure imgb0002
     in the cat a cation exchangeable with calcium of the valence n, x is a number from 0.7 to 1.5, Me boron or aluminum and y is a number from 0.8 to 6, and
  • B) as a dispersing component 0.5 to 6% by weight, preferably 1 to 2% by weight, in particular 1.4 to 1.6% by weight, a mixture of at least two different alkylphenol ethoxylates of the formula
    Figure imgb0003
     contains.

In der Formel II kann R= ein aliphatischer Rest mit 1 bis 15, beispielsweise -CH3, -C2H5, Propyl, Butyl, Pentyl, Hexyl-, Heptyl-, Octyl- und Nonyl vorzugsweise mit 9 C-Atomen wie Nonyl sein. Der Rest R kann in ortho, meta oder/und paraStellung subsitutiert sein. So können auch Gemische eingesetzt werden, in denen neben p-substituiertem Arylring auch o-substituierter Benzolring vorhanden ist. Vorzugsweise werden Gemische eingesetzt, in denen zu 90 % eine p-Substitution und zu 10 % eine ortho-Substitution vorliegt.In formula II, R = an aliphatic radical with 1 to 15, for example -CH 3 , -C 2 H 5 , propyl, butyl, pentyl, hexyl, heptyl, octyl and nonyl, preferably with 9 carbon atoms such as nonyl be. The radical R can be substituted in the ortho, meta and / or para position. It is also possible to use mixtures in which, in addition to p-substituted aryl rings, o-substituted benzene rings are also present. Mixtures are preferably used in which there is 90% p-substitution and 10% ortho-substitution.

n kann bei dem einen in der Mischung verwendeten Alkylphenoläthoxylat 2 bis 7, vorzugsweise 4 bis 6, insbesondere 5 und bei dem anderen Alkylphenoläthoxylat 8 bis 15, vorzugsweise 8 bis 12, insbesondere 9 oder 10 bedeuten. n kann aber auch bei Gemischen der Alkylphenolate jeweils 7 oder 9 oder 12 bedeuten.n can mean 2 to 7, preferably 4 to 6, in particular 5 in the case of one alkylphenol ethoxylate used in the mixture and 8 to 15, preferably 8 to 12, in particular 9 or 10 in the other alkylphenol ethoxylate. However, n can also mean 7 or 9 or 12 in the case of mixtures of the alkylphenolates.

In der erfindungsgemäßen Suspension kann die Komponente A kristallin sein.In the suspension according to the invention, component A can be crystalline.

In der Formel I der Komponente A kann y eine Zahl von 1,3 bis 4 bedeuten.In formula I of component A, y can be a number from 1.3 to 4.

Die kristalline Komponente A kann in einer bevorzugten Ausführungsform ein Zeolith des Typs A sein.In a preferred embodiment, crystalline component A can be a type A zeolite.

Die vorstehend genannten Verbindungen sind die wesentlichen Bestandteile der erfindungsgemäßen Suspension. Es können jedoch auch weitere Bestandteile enthalten sein, so z.B. schaumdämpfende Zusätze bzw. sogenannte Lösungsvermittler, d.h. Verbindungen, die die Löslichkeit der zugesetzten Dispergiermittel in der wässrigen Phase verbessern. Als Schaumdämpfer können die üblichen schaumdämpfenden Substanzen, beispielsweise schaumdämpfende Seife, Silikonentschäumer, schaumdämpfende Triazinderivate, die sämtlich der Fachwelt bekannt und geläufig sind, eingesetzt werden. Ein derartiger Zusatz ist im allgemeinen nicht erforderlich; bei schäumenden Dispergiermitteln kann er jedoch - insbesondere bei höheren Alkylbenzolsulfonsäure-Einsatzmengen - erwünscht sein.The above-mentioned compounds are the essential components of the suspension according to the invention. However, other ingredients may also be included, e.g. foam-suppressing additives or so-called solubilizers, i.e. Compounds that improve the solubility of the added dispersants in the aqueous phase. The usual foam-suppressing substances, for example foam-suppressing soap, silicone defoamers, foam-suppressing triazine derivatives, all of which are known and familiar to the expert, can be used as foam suppressors. Such an addition is generally not necessary; in the case of foaming dispersants, however, it may be desirable, especially when using higher amounts of alkylbenzenesulfonic acid.

Auch ein Zusatz von lösungsvermittelnden Substanzen ist im allgemeinen nicht erforderlich, kann jedoch angezeigt sein, wenn die erfindungsgemäße Suspension als stabilisierendes Mittel ein hydrophiles, aber wenig in Wasser lösliches Kolloid wie beispielsweise Polyvinylalkohol enthält. Vorteilhaft wird z.B. ein Lösungsvermittler - sehr geeignet ist Dimethylsulfoxid - eingesetzt, wenn die Einsatzkonzentration eines in Wasser nur wenig löslichen Stabilisierungsmittels der Gruppe 1 höher ist als etwa 1 %. Der Anteil des Lösungsvermittlers an der Gesamtsuspension kann beispielsweise in der gleichen Größenordnung wie der Anteil des Stabilisierungs-The addition of solubilizing substances is generally not necessary, but it may be appropriate if the suspension according to the invention contains a hydrophilic, but sparingly water-soluble colloid, such as polyvinyl alcohol, as a stabilizing agent. It is advantageous e.g. a solubilizer - dimethyl sulfoxide is very suitable - if the concentration of a stabilizing agent of group 1, which is only slightly soluble in water, is higher than about 1%. The proportion of the solubilizer in the total suspension can, for example, be of the same order of magnitude as the proportion of the stabilizing agent.

mittels liegen. Weitere als Lösungsvermittler geeignete Verbindungen sind der Fachwelt allgemein bekannt; hydrotrophe Mittel wie beispielsweise Benzolsulfonsäure, Toluolsulfonsäure, Xylolsulfonsäure bzw. deren wasserlösliche Salze oder auch Octylsulfat sind geeignet.by lying. Other compounds suitable as solubilizers are generally known to the expert; Hydrotrophic agents such as, for example, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid or their water-soluble salts or also octyl sulfate are suitable.

Bei sämtlichen Angaben zur "Konzentration der Aluminiumsilikate" zum "Feststoffgehalt" oder zum Gehalt an "Aktivsubstanz" (=AS) wird auf den Zustand der Aluminiumsilikate Bezug genommen, der nach einstündigem Trocknen bei 800°C erreicht wird. Bei dieser Trocknung wird das anhaftende und das gebundene Wasser praktisch völlig entfernt.With all information on the "concentration of aluminum silicates" on the "solids content" or on the content of "active substance" (= AS ), reference is made to the state of the aluminum silicates, which is reached after drying for one hour at 800 ° C. During this drying, the adhering and bound water is practically completely removed.

Bei den einzusetzenden Aluminiumsilikaten der Komponente A kann es sich um amorphe oder um kristalline Produkte handeln, wobei selbstverständlich auch Mischungen von amorphen und kristallinen Produkten und auch teilkristalline Produkte einsetzbar sind. Die Aluminiumsilikate können natürlich vorkommende oder aber synthetisch hergestellte Produkte sein, wobei die synthetisch hergestellten Produkte bevorzugt sind. Die Herstellung kann z:B. durch Reaktion von wasserlöslichen Silikaten mit wasserlöslichen Aluminaten in Gegenwart von Wasser erfolgen. Zu diesem Zweck können wässrige Lösungen der Ausgangsmaterialien miteinander vermischt oder eine in festem Zustand vorliegende Komponente mit der anderen, als wässrige Lösung vorliegenden Komponente umgesetzt werden. Auch durch Vermischen beider, in festem Zustand vorliegender Komponente erhält man bei Anwesenheit von Wasser die gewünschten Aluminiumsilikate. Auch aus A1(OH)2, Al2O3 oder SiO2 lassen sich durch Umsetzen mit Alkalisilikat- bzw. aluminatlösungen Aluminiumsilikate herstellen. Die Herstellung kann auch nach weiteren bekannten Verfahren erfolgen. Insbesondere bezieht sich die Erfindung auf Aluminiumsilikate, die eine dreidimensionale Raumgitterstruktur aufweisen.The aluminum silicates of component A to be used can be amorphous or crystalline products, although mixtures of amorphous and crystalline products and also partially crystalline products can of course also be used. The aluminum silicates can be naturally occurring or else synthetically produced products, the synthetically produced products being preferred. The production can, for example: by reaction of water-soluble silicates with water-soluble aluminates in the presence of water. For this purpose, aqueous solutions of the starting materials can be mixed with one another or a component present in the solid state can be reacted with the other component present as an aqueous solution. The desired aluminum silicates are also obtained by mixing the two components present in the solid state in the presence of water. Aluminum silicates can also be produced from A1 (OH) 2 , Al 2 O 3 or SiO 2 by reaction with alkali silicate or aluminate solutions. The production can also be carried out by other known processes. In particular relates the invention relates to aluminum silicates which have a three-dimensional space lattice structure.

Das bevorzugte, etwa im Bereich von 100 bis 200 mg CaO/g AS meist bei etwa 100 bis 180 mg CaO/g AS liegende Calciumbindevermögen findet sich vor allem bei Verbindungen der Zusammensetzung:

Figure imgb0004
The preferred calcium binding capacity, which is approximately in the range from 100 to 200 mg CaO / g AS, usually around 100 to 180 mg CaO / g AS, is found above all in compounds of the composition:
Figure imgb0004

Diese Summenformel umfaßt zwei Typen verschiedener Kristallstrukturen (bzw. deren nicht kristalline Vorprodukte), die sich auch durch ihre Summenformeln unterscheiden.'Es sind dies:

Figure imgb0005
Figure imgb0006
 This empirical formula comprises two types of different crystal structures (or their non-crystalline precursors), which also differ in their empirical formulas.
Figure imgb0005
Figure imgb0006

Die unterschiedlichen Kristallstrukturen zeigen sich im Röntgenbeugungsdiagramm.The different crystal structures are shown in the X-ray diffraction diagram.

Das in wässriger Suspension vorliegende amorphe oder kristalline Aluminiumsilikat läßt sich durch Filtration von der verbleibenden wässrigen Lösung abtrennen und bei Temperaturen von z.B. 50 bis 400°C trocknen. Je nach den Trocknungsbedingungen enthält das Produkt mehr oder weniger gebundenes Wasser.The amorphous or crystalline aluminum silicate present in aqueous suspension can be separated from the remaining aqueous solution by filtration and at temperatures of e.g. Dry 50 to 400 ° C. Depending on the drying conditions, the product contains more or less bound water.

Derart hohe Trocknungstemperaturen sind im allgemeinen nicht zu empfehlen; zweckmäßigerweise geht man nicht über 200°C hinaus, wenn das Aluminiumsilikat für den Einsatz in Wasch-und Reinigungsmitteln vorgesehen ist. Die Aluminiumsilikate brauchen jedoch nach ihrer Herstellung zur Bereitung einer erfindungsgemäßen Suspension überhaupt nicht getrocknet zu werden; vielmehr kann - und dies ist besonders vorteilhaft - ein von der Herstellung noch feuchtes Aluminiumsilikat verwendet werden. Es lassen sich jedoch auch bei mittleren Temperaturen, beispielsweise bei 80 bis 200°C, bis zur Entfernung des anhaftenden flüssigen Wassers getrocknete Aluminiumsilikate zur Bereitung erfindungsgemäßer Suspensionen verwenden.Such high drying temperatures are generally not recommended; Expediently, the temperature does not exceed 200 ° C. if the aluminum silicate is intended for use in detergents and cleaning agents. However, after their preparation, the aluminum silicates do not need to be dried at all to prepare a suspension according to the invention will; rather - and this is particularly advantageous - an aluminum silicate that is still moist from manufacture can be used. However, it is also possible to use dried aluminum silicates at medium temperatures, for example at 80 to 200 ° C., until the adhering liquid water has been removed, in order to prepare suspensions according to the invention.

Die Teilchengröße der einzelnen Aluminiumsilikatpartikel kann verschieden sein und z.B. im Bereich zwischen 0,1 µ und 0,1 mm liegen. Diese Angabe bezieht sich auf die Primärteilchengröße, d.h. die Größe der bei der Fällung und gegebenenfalls der anschließenden Kristallisation anfallenden Teilchen. Mit besonderem Vorteil verwendet man Aluminiumsilikate, die zu wenigstens 80 Gew.-% aus Teilchen einer Größe von 10 bis 0.01 µ, insbesondere von 8 bis 0.1 g bestehen.The particle size of the individual aluminum silicate particles can be different and e.g. are in the range between 0.1 µ and 0.1 mm. This refers to the primary particle size, i.e. the size of the particles obtained during the precipitation and, if appropriate, the subsequent crystallization. It is particularly advantageous to use aluminum silicates which consist of at least 80% by weight of particles with a size of 10 to 0.01 μ, in particular 8 to 0.1 g.

Vorzugsweise enthalten diese Aluminiumsilikate keine Primär- bzw. Sekundärteilchen mehr mit Durchmessern oberhalb von 45 Als Sekundärteilchen werden Teilchen, die durch Agglomeration der Primärteilchen zu größeren Gebilden entstanden sind, bezeichnet.These aluminum silicates preferably no longer contain primary or secondary particles with diameters above 45. Secondary particles are particles which are formed by agglomeration of the primary particles into larger structures.

Im Hinblick auf die Agglomeration der Primärteilchen zu größer Gebilden hat sich die Verwendung der von ihrer Herstellung noch feuchten Aluminiumsilikate zur Herstellung der erfindungs gemäßen Suspensionen besonders bewährt, da sich herausgestellt hat, daß bei Verwendung dieser noch feuchten Produkte eine Bildung von Sekundärteilchen praktisch vollständig unterbunden wird.With regard to the agglomeration of the primary particles to form larger structures, the use of the aluminum silicates which are still moist from their preparation for the preparation of the suspensions according to the invention has proven particularly useful since it has been found that the formation of secondary particles is practically completely prevented when these still moist products are used .

In einer besonders bevorzugten Ausführungsform der Erfindung wird als Komponente A pulverförmiger Zeolith des Typs A mit besonders definiertem Teilchenspektrum eingesetzt.In a particularly preferred embodiment of the invention, powdered zeolite of type A with a particularly defined particle spectrum is used as component A.

Derartige Zeolithpulver können gemäß DE-AS 24 47 021, DE-AS 25 17 218, DE-OS 26 52 419, DE-OS 26 51 420, DE-OS 26 51 436 DE-OS 26 51 437, DE-OS 26 51 445, DE-OS 26 51 485 hergestellt werden. Sie weisen dann die dort angegebenen Teilchenverteilungskurven auf.Such zeolite powder can according to DE-AS 24 47 021, DE-AS 25 17 218, DE-OS 26 52 419, DE-OS 26 51 420, DE-OS 26 51 436 D E-OS 26 51 437, DE-OS 26 51 445, DE-OS 26 51 485 are produced. They then have the particle distribution curves given there.

In einer besonders bevorzugten Ausführungsform kann ein pulverförmiger Zeolith des Typs A verwendet werden, der die in der DE-OS 26 51 485 beschriebene Teilchengrössenverteilung aufweist.In a particularly preferred embodiment, a powdery zeolite of type A can be used, which has the particle size distribution described in DE-OS 26 51 485.

Die Konzentration an Komponente A kann bevorzugt 44 bis 55 Gew.-%, insbesondere 46 bis 52 Gewichtsprozent und mehr betragen.The concentration of component A can preferably be 44 to 55% by weight, in particular 46 to 52% by weight or more.

Die Komponente B kann eine Mischung aus mindestens zwei Alkylphenoläthoxylaten der Formel

Figure imgb0007
sein. Dabei kann der Phenolring sowohl in para- als auch in ortho-Stellung substituiert sein. Die Alkylphenoläthoxylate können in beliebiger Mischung, vorzugsweise in einem Verhältnis von 1:9 bis 9:1, vorzugsweise 2:3 bis 3:2, insbesondere 0,9:1,1 bis 1,1:0,9 eingesetzt werden. Dabei entsprechen diese Alkylphenoläthoxylate insbesondere der Formel II in der R = Nonyl und n = 5 bzw. 9 bedeuten.Component B can be a mixture of at least two alkylphenol ethoxylates of the formula
Figure imgb0007
 be. The phenol ring can be substituted both in the para and in the ortho position. The alkylphenol ethoxylates can be used in any mixture, preferably in a ratio of 1: 9 to 9: 1, preferably 2: 3 to 3: 2, in particular 0.9: 1.1 to 1.1: 0.9. These alkylphenol ethoxylates correspond in particular to the formula II in which R = nonyl and n = 5 and 9, respectively.

Die Konzentration dieser Mischung in der wässrigen Suspension kann vorzugsweise von 1 bis 2 Gew.-%, insbesondere 1,4 bis 1,6 G.-% betragen. Diese Konzentration ist ausreichend, eine Suspension mit einem Feststoffgehalt von 50 Gew.-% und mehr zu stabilisieren.The concentration of this mixture in the aqueous suspension can preferably be from 1 to 2% by weight, in particular 1.4 to 1.6% by weight. be. This concentration is sufficient to stabilize a suspension with a solids content of 50% by weight or more.

Die erfindungsgemäße Suspension weist den Vorteil auf, daß sie in dem Temperaturbereich von 10 bis 50°C sedimentationsstabil ist und eine pumpfähige Konsistenz aufweist.The suspension according to the invention has the advantage that it is stable to sedimentation in the temperature range from 10 to 50 ° C. and has a pumpable consistency.

Von weiterem Vorteil ist, daß das Alkylphenoläthoxylat bei Raumtemperatur flüssig ist und daher nicht aufgeheizt werden braucht.A further advantage is that the alkylphenol ethoxylate is liquid at room temperature and therefore does not need to be heated.

Von besonderem Vorteil ist, daß in der erfindungsgemäßen Suspension deutlich höhere Feststoffgehalte von 50 Gew.-% und mehr erreicht werden können.It is particularly advantageous that significantly higher solids contents of 50% by weight and more can be achieved in the suspension according to the invention.

Die bekannte Suspension weist eine geringere Sedimentationsstabilität auf und ist bei gleicher Einarbeitungsart bei Raumtemperatur nicht homogen und deshalb schlechter verarbeitbar.The known suspension has a lower sedimentation stability and, with the same type of incorporation, is not homogeneous at room temperature and is therefore more difficult to process.

Grundsätzlich können die wässrigen Suspensionen außer den genannten Bestandteilen A und B und außer gegebenenfalls von Ausgangsmaterialien für die Herstellung dieser Bestandteile noch verbleibenden Stoffen auch weitere Bestandteile in vergleichsweise geringen Mengen enthalten. Ist eine Weiterverarbeitung der Suspension zu Wasch- und Reinigungsmitteln vorgesehen, so handelt es sich bei den zusätzlich vorliegenden Stoffen natürlich zweckmässigerweise um Stoffe, die als Bestandteile von Wasch- und Reinigungsmitteln geeignet sind.In principle, the aqueous suspensions can contain, in addition to the constituents A and B mentioned and, in addition to any starting materials for the production of these constituents, any remaining constituents, further constituents in comparatively small amounts. If the suspension is to be further processed into detergents and cleaning agents, the additional substances present are of course expediently substances which are suitable as constituents of detergents and cleaning agents.

Einen Anhaltspunkt über die Stabilität der Suspensionen gibt ein einfacher Test, bei welchem eine Aluminiumsilikatsuspension der gewünschten Konzentration - z.B. 31 %ig - hergestellt wird, die ein erfindungsgemäßes Dispergiermittel und gegebenenfalls weitere Stoffe, beispielsweise Waschmittelbestandteile wie Pentanatriumtriphosphat, in verschiedenen Mengen enthält. Der Einfluß des zugesetzten Stoffes kann dann im Absetzverhalten der Suspension visuell beobachtet werden. Nach 24stündigem Stehen soll eine bevorzugte Suspension im allgemeinen höchstens so weit abgesetzt sein, daß die überstehende klare bzw. von Silikatteilchen freie Lösung nicht mehr als 20 %, vorzugsweise nicht mehr als 10 %, insbesondere nicht mehr als 6 % der Gesamthöhe ausmacht. Im allgemeinen soll die Menge der Zusatzstoffe so gehalten werden, daß die Suspension nach 12stündigem, vorzugsweise nach 24stündigem und insbesondere auch nach 48stündigem Stehen in Vorratsbehälter und Rohr- bzw. Schlauchleitungen noch einwandfrei wieder umgepumpt werden kann. Das Absetzverhalten der gegebenenfalls noch weitere Bestandteile enthaltenden Suspension wird bei Raumtemperatur - bei einer Gesamthöhe der Suspension von 10 cm - geprüft. Sie sind auch nach 4.bzw. 8 Tagen einwandfrei pumpfähig. Auch diese Angaben zur Suspensionsstabilität geben nur Anhaltspunkte; es hängt vom jeweiligen Einzelfall ab, welche Suspensionsstabilität einzustellen ist. Bei Verwendung der erfindungsgemäßen Suspension als Stammsuspension zur längeren La-gerung in einem Reservoir, aus welchem sie nach Bedarf durch Pumpen abgezogen werden kann, kann es zweckmäßig sein, den Anteil sonstiger Bestandteile beispielsweise von Wasch-und Reinigungsmitteln gering zu halten oder auf diese ganz zu verzichten.An indication of the stability of the suspensions is provided by a simple test in which an aluminum silicate suspension of the desired concentration - for example 31% strength - is produced, which contains a dispersant according to the invention and optionally other substances, for example detergent constituents such as pentasodium triphosphate, in different amounts. The influence of the added substance can then be visually observed in the settling behavior of the suspension. After standing for 24 hours, a preferred suspension should generally be at most so far removed that the protruding clear or silicate-free solution does not make up more than 20%, preferably not more than 10%, in particular not more than 6% of the total height. In general, the amount of additives should be kept such that the suspension can still be pumped over again properly after 12 hours, preferably after 24 hours and in particular also after 48 hours in the storage container and pipe or hose lines. The settling behavior of the suspension, which may also contain other constituents, is checked at room temperature - with a total height of the suspension of 10 cm. They are also after 4. or Fully pumpable for 8 days. Also this information to the suspension stability only give A nhaltspunkte; It depends on the individual case which suspension stability is to be set. When using the suspension according to the invention as a stock suspension to the longer L a delay in a reservoir from which it can be withdrawn by pumping as required, it may be desirable to keep the proportion of other components, for example, of detergents and cleaning agents is low or in this very to renounce.

Die Suspensionen können durch einfaches Vermischen ihrer Bestandteile hergestellt werden, wobei die Aluminiumsilikate z.B. als solche oder - gegebenenfalls von der Herstellung her - bereits feucht bzw. in wässriger Suspension befindlich eingesetzt werden können. Besonders vorteilhaft ist es, die von ihrer Herstellung her noch feuchten Aluminiumsilikate z.B. als Filterkuchen in die Komponente B einzurühren.The suspensions can be prepared by simply mixing their constituents, the aluminum silicates e.g. can be used as such or - if necessary from the production stage - already moist or in an aqueous suspension. It is particularly advantageous to use aluminum silicates that are still moist, e.g. stir into component B as a filter cake.

Es können aber selbstverständlich auch bereits getrocknete, d.h. von anhaftendem Wasser befreite, gegebenenfalls noch gebundenes Wasser aufweisende Aluminiumsilikate eingesetzt werden.However, it is of course also possible to use dried, i.e. Aluminum silicates freed from adhering water and possibly still containing water can be used.

Die erfindungsgemäßen Suspensionen zeichnen sich durch hohe Stabilität und durch weitere Vorteile aus. Ihre stabilisierende Wirkung ist insbesondere bei Aluminiumsilikaten mit Teilchengrößen von 5 bis 30 p. besonders wertvoll. Sie sind pumpbar, so daß sie eine einfache Handhabung feuchter Aluminiumsilikate ermöglichen. Selbst nach längeren Unterbrechungen im Pumpvorgang sind die Suspensionen einwandfrei umpumpbar. Auf Grund ihrer hohen Stabilität sind die Suspensionen auch in üblichen Tank- und Kesselwagen transportierbar, ohne daß dabei eine Bildung unbrauchbarer bzw. störender Rückstände zu befürchten ist. Damit sind die Suspensionen hervorragend als eine Lieferform von Aluminiumsilikaten für die Lieferung an beispielsweise Waschmittelhersteller geeignet.The suspensions according to the invention are distinguished by high stability and by further advantages. Their stabilizing effect is particularly in the case of aluminum silicates with particle sizes of 5 to 30 p. particularly valuable. They are pumpable so that they allow easy handling of moist aluminum silicates. The suspensions can be pumped around perfectly even after long interruptions in the pumping process. Because of their high stability, the suspensions can also be transported in conventional tank and tank wagons without fear of the formation of unusable or disruptive residues. This makes the suspensions ideal as a form of delivery of aluminum silicates for delivery to detergent manufacturers, for example.

Die Suspensionen lassen sich bei Raumtemperatur oder auch bei höheren Temperaturen aufbewahren, durch Rohrleitungen pumpen oder auf andere Weise transportieren. Meist erfolgt die Handhabung der Suspensionen bei Temperaturen zwischen Raumtemperatur - meist bevorzugt - und etwa 60°C.The suspensions can be stored at room temperature or at higher temperatures, pumped through pipes or transported in some other way. Mostly done the handling of the suspensions at temperatures between room temperature - usually preferred - and about 60 ° C.

Besonders geeignet sind die erfindungsgemäßen Suspensionen für die Weiterverarbeitung zu trocken erscheinenden, schütt- bzw. rieselfähigen Produkten, also beispielsweise zur Herstellung von pulverförmigen Wasserenthärtungsmitteln, z.B. auf dem Wege der Sprühtrocknung, geeignet. Damit sind die Suspensionen von erheblicher Bedeutung bei der Herstellung von pulverförmigen Aluminiumsilikaten. Es treten keine lästigen Rückstände bei der Zufuhr der wäßrigen Suspensionen zur Trocknungsapparatur auf. Ferner hat sich gezeigt, daß die Suspensionen der Erfindung eine Verarbeitung zu außerordentlich staubfreien Produkten ermöglichen.The suspensions according to the invention are particularly suitable for further processing to appear dry, pourable or free-flowing products, for example for the production of powdered water softeners, e.g. by spray drying. The suspensions are therefore of considerable importance in the production of powdered aluminum silicates. There are no annoying residues when feeding the aqueous suspensions to the drying apparatus. It has also been shown that the suspensions of the invention enable processing to extremely dust-free products.

Auf Grund ihrer besonderen Stabilität sind die erfindungsgemäßen Suspensionen bereits als solche, d.h. ohne weitere Verarbeitung mit oder ohne weitere waschend, bleichend und/ oder reinigend wirkende Zusätze, beispielsweise als Wasserenthärtungsmittel, Wasch- oder Reinigungsmittel und insbesondere als flüssige Scheuermittel mit erhöhter Suspensionsstabilität verwendbar.Due to their particular stability, the suspensions according to the invention are already as such, i.e. usable without further processing with or without further washing, bleaching and / or cleaning additives, for example as water softening agents, washing or cleaning agents and in particular as liquid abrasives with increased suspension stability.

Eine besonders wichtige Verwendung der Suspension ist die Weiterverarbeitung zu trocken erscheinenden, schütt- bzw. rieselfähigen Wasch- und Re.inigungsmitteln, die neben den Suspensionsbestandteilen weitere Verbindungen enthalten.A particularly important use of the suspension is the further processing into dry-appearing, free-flowing or free-flowing detergents and cleaning agents which contain further compounds in addition to the suspension components.

Die erfindungsgemäßen Suspensionen sind insbesondere zur Herstellung von pulverförmigen Wasch- und Reinigungsmitteln geeignet.The suspensions according to the invention are particularly suitable for the production of powder detergents.

Zur Herstellung dieser Mittel geht man von einer wäßrigen, fließfähigen Vormischung der einzelnen Bestandteile der Mittel aus und führt diese auf übliche Weise in ein schüttfähiges Produkt über. Dabei werden die oben definierten Aluminiumsilikate in Form der erfindungsgemäßen Suspension eingesetzt. Die erfindungsgemäßen Suspensionen können nach beliebigen bekannten Verfahren zu den festen, schüttfähigen Wasch- und Reinigungsmitteln verarbeitet werden.To prepare these agents, an aqueous, flowable premix of the individual constituents of the agents is used and these are converted into a pourable product in the usual way. The aluminum silicates defined above are used in the form of the suspension according to the invention. The suspensions according to the invention can be processed into solid, pourable detergents and cleaning agents by any known method.

Insbesondere geht man bei der Herstellung von pulverförmigen, rieselfähigen Wasch- und Reinigungsmitteln so vor, daß man eine erfindungsgemäße Suspension - beispielsweise aus einem Vorratsbehälter - mit wenigstens einem waschend, bleichend oder reinigend wirkenden Bestandteil des herzustellenden Mittels vermischt und das Gemisch anschließend nach einem beliebigen Verfahren in das pulverförmige Produkt überführt. Vorteilhaft wird ein Komplexbildner zugesetzt, d.h. eine Verbindung, die die für die Wasserhärte verantwortlichen Erdalkalimetallionen, insbesondere Magnesium- und Calciumionen komplex zu binden vermag.In particular, in the production of powdery, free-flowing detergents and cleaning agents, a suspension according to the invention - for example from a storage container - is mixed with at least one detergent, bleaching or cleaning component of the agent to be prepared, and the mixture is then mixed by any process converted into the powdered product. A complexing agent is advantageously added, i.e. a compound that is able to complexly bind the alkaline earth metal ions responsible for water hardness, especially magnesium and calcium ions.

Im allgemeinen wird bei der Herstellung von Wasch- und Reinigungsmitteln die erfindungsgemäße Suspension vorzugsweise mit wenigstens einem nicht zu den möglichen Bestandteilen der Komponente B gehörenden wasserlöslichen Tensid vereinigt.In general, in the production of detergents and cleaning agents, the suspension according to the invention is preferably combined with at least one water-soluble surfactant which does not belong to the possible components of component B.

Bei der Herstellung von Wasch- und Reinigungsmitteln gibt es verschiedene Varianten.There are different variants in the manufacture of detergents and cleaning agents.

Beispielsweise können die erfindungsgemäßen Suspensionen mit zur Bindung von Kristallwasser befähigten Substanzen vereinigt werden, zweckmäßigerweise durch Aufsprühen der Suspension auf die in einem Mischer vorgelegten, zur Bindung von Kristallwasser befähigten Verbindungen, so daß bei ständigem Durchmischen ein schließlich festes, trocken erscheinendes Produkt erhalten wird. Vorzugsweise werden die erfindungsgemäßen Suspensionen jedoch, als "Slurry" vermischt, mit wenigstens einer weiteren waschend, bleichend oder reinigend wirkenden Verbindung der Zerstäubungstrocknung unterworfen. Hierbei zeigen sich weitere überraschende Vorteile der beanspruchten Aluminiumsilikat-Suspension. Es hat sich nämlich gezeigt, daß bei Einsatz erfindungsgemäßer Suspensionen bei der Zerstäubungstrocknung sehr staubarme Produkte erhalten werden können. Die durch Zerstäubungstrocknung erhaltenen Produkte weisen ein hohes Calciumbindevermögen auf und sind gut benetzbar.For example, the suspensions according to the invention can be used with substances capable of binding water of crystallization be combined, expediently by spraying the suspension onto the compounds which are present in a mixer and are capable of binding water of crystallization, so that a constant solid, dry-appearing product is obtained with constant mixing. Preferably, however, the suspensions according to the invention, mixed as a "slurry", are subjected to the atomization drying with at least one further washing, bleaching or cleaning compound. This shows further surprising advantages of the claimed aluminum silicate suspension. It has been shown that very low-dust products can be obtained when using suspensions according to the invention in the spray drying. The products obtained by spray drying have a high calcium binding capacity and are easily wettable.

Waschmittel, die unter Verwendung der oben beschriebenen Suspension hergestellt worden sind, können auf verschiedenste Weise zusammengesetzt sein. Im allgemeinen enthalten sie wenigstens ein nicht zu den erfindungsgemäß eingesetzten Dispergiermitteln, die in den beanspruchten AluminiumsilikatSuspensionen vorliegen, gehörendes wasserlösliches Tensid. Allgemein enthalten sie neben wenigstens einer weiteren Verbindung, die waschend, bleichend oder reinigend wirkt und anorganisch oder organisch ist, als Calcium bindende Verbindung ein wie oben definiertes Aluminiumsilikat. Darüber hinaus können in derartigen Mitteln sonstige übliche, meist in geringeren Mengen anwesende Hilfs- und Zusatzstoffe vorhanden sein.Detergents which have been produced using the suspension described above can be composed in various ways. In general, they contain at least one water-soluble surfactant which does not belong to the dispersants used according to the invention and which are present in the claimed aluminum silicate suspensions. In general, in addition to at least one further compound which has a washing, bleaching or cleaning action and is inorganic or organic, they contain an aluminum silicate as defined above as a calcium-binding compound. In addition, other customary auxiliaries and additives, which are usually present in smaller amounts, can be present in such agents.

BeispieleExamples

Es wird ein Zeolit-A-Filterkuchen mit Wasser und Stabilisator verrührt.A Zeolit-A filter cake is mixed with water and stabilizer.

Als Stabilisator werden Verbindungen entsprechend der Formel II, wobei n = 5,9 und 10 und R = Nonyl- bedeuten, verwendet. Angegeben wird der Äthoxylierungsgrad EO. Der eingesetzte Zeolith-A-Filterkuchen wird gemäß DE-OS 26 51 485 hergestellt und weist das dort angegebene Teilchenspektrum auf.

Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
 Compounds corresponding to formula II, where n = 5.9 and 10 and R = nonyl-, are used as stabilizers. The degree of ethoxylation EO is given. The zeolite A filter cake used is produced according to DE-OS 26 51 485 and has the particle spectrum specified there.
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012

Bei den folgenden Beispielen 26 bis 37 werden Verbindungen der Formel II, wobei n = 5,9,7 und 12 und R = Nonyl- und Octyl- bedeuten kann.In the following examples 26 to 37, compounds of the formula II, where n = 5,9,7 and 12 and R = nonyl- and octyl- can mean.

Der eingesetzte Zeolith A ist identisch mit dem der vorangestellten Beispiele 1 bis 25.

Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
 The zeolite A used is identical to that of Examples 1 to 25 above.
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016

Claims (7)

1. Wässrige pumpfähige, stabile Suspensionen eines wasserunlöslichen, zum Binden von Calciumionen befähigten Silikates, dadurch gekennnzeichnet, daß sie, bezogen auf das Gesamtgewicht der wässrigen Suspension A) als zum Binden von Calcium befähigtes Silikat 0,5 bis 80 Gewichtsprozent einer feinverteilten, gebundenes Wasser enthaltenden, synthetisch hergestellten, wasserunlöslichen Verbindung der allgemeinen Formel
Figure imgb0017
in der Kat.ein mit Calcium austauschbares Kation der Wertigkeit n, x eine Zahl von 0,7 bis 1,5, Me Bor oder Aluminium und y eine Zahl von 0,8 bis 6 bedeuten und B) als dispergierend wirkenden Bestandteil 0,5 bis 6 Gewichtsprozent eine Mischung von mindestens zwei verschiedenen Alkylphenoläthoxylaten der Formel
Figure imgb0018
enthält. 1. Aqueous pumpable, stable suspensions of a water-insoluble silicate capable of binding calcium ions, characterized in that they are based on the total weight of the aqueous suspension A) as a silicate capable of binding calcium 0.5 to 80 percent by weight of a finely divided, bound water-containing, synthetically produced, water-insoluble compound of the general formula
Figure imgb0017
 in cat. a cation exchangeable with calcium of the valence n, x is a number from 0.7 to 1.5, Me boron or aluminum and y is a number from 0.8 to 6 and B) as a dispersing component 0.5 to 6 percent by weight, a mixture of at least two different alkylphenol ethoxylates of the formula
Figure imgb0018
 contains. 2. Suspension nach Anspruch 1, dadurch gekennzeichnet, daß die Komponente A kristallin ist.2. Suspension according to claim 1, characterized in that component A is crystalline. 3. Suspension nach den Ansprüchen 1 oder 2, dadurch gekennzeichnet, daß in der Formel I der Komponente A y eine Zahl von 1,3 bis 4 bedeutet.3. Suspension according to claims 1 or 2, characterized in that in formula I of component A y is a number from 1.3 to 4. 4. Suspension nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß die Komponente A ein Zeolith A ist.4. Suspension according to claims 1 to 3, characterized in that component A is a zeolite A. 5. Suspension nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß die Komponente B aus einer Mischung von zwei Alkylphenoläthoxylaten der Formel II, besteht in der bei dem einen Alkylphenoläthoxylat n = 2 bis 7 und bei dem anderen Alkylphenoläthoxylat n = 8 bis 15 bedeutet.5. Suspension according to claims 1 to 4, characterized in that component B consists of a mixture of two alkylphenol ethoxylates of the formula II, in which in one alkylphenol ethoxylate n = 2 to 7 and in the other alkylphenol ethoxylate n = 8 to 15 . 6. Suspension nach Anspruch 5, dadurch gekennzeichnet, daß das Mischungsverhältnis der beiden Alkylphenoläthoxylate 1:9 bis 9:1 beträgt.6. Suspension according to claim 5, characterized in that the mixing ratio of the two alkylphenol ethoxylates is 1: 9 to 9: 1. 7. Verwendung der wässrigen Suspension nach den Ansprüchen 1 bis 6 zur Herstellung pulverförmiger Wasch- und Reinigungsmittel.7. Use of the aqueous suspension according to claims 1 to 6 for the production of powder detergents.
EP83100470A 1982-03-17 1983-01-20 Aqueous stable suspensions of water-insoluble silicates capable of binding calciumions, and their use in the production of washing and cleaning agents Expired EP0088866B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83100470T ATE20537T1 (en) 1982-03-17 1983-01-20 AQUEOUS STABLE SUSPENSION OF WATER-INSOLUBLE SILICATES CAPABLE OF BINDING CALCIUM IONS AND THEIR USE IN THE MANUFACTURE OF DETERGENT AND CLEANING AGENTS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3209631A DE3209631A1 (en) 1982-03-17 1982-03-17 AQUEOUS, STABLE SUSPENSION OF WATER-INSOLUBLE SILICATES CAPABLE OF CALCIUMIONS AND THE USE THEREOF FOR THE PRODUCTION OF DETERGENT AND CLEANING AGENTS
DE3209631 1982-03-17

Publications (2)

Publication Number Publication Date
EP0088866A1 true EP0088866A1 (en) 1983-09-21
EP0088866B1 EP0088866B1 (en) 1986-06-25

Family

ID=6158458

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83100470A Expired EP0088866B1 (en) 1982-03-17 1983-01-20 Aqueous stable suspensions of water-insoluble silicates capable of binding calciumions, and their use in the production of washing and cleaning agents

Country Status (13)

Country Link
US (1) US4486331A (en)
EP (1) EP0088866B1 (en)
JP (1) JPS58168698A (en)
KR (1) KR910001604B1 (en)
AT (1) ATE20537T1 (en)
BR (1) BR8301254A (en)
CA (1) CA1200456A (en)
DE (2) DE3209631A1 (en)
DK (1) DK158520C (en)
ES (1) ES8505832A1 (en)
FI (1) FI830493L (en)
NO (1) NO830511L (en)
SU (1) SU1443805A3 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3401861A1 (en) * 1983-09-06 1985-03-21 Degussa Ag, 6000 Frankfurt AQUEOUS, STABLE SUSPENSION OF WATER-INSOLUBLE SILICATES ENABLED TO CALCIUMIONS, THEIR USE FOR THE PRODUCTION OF PHOSPHATE SUBSTITUTES FOR WASHING AND CLEANING AGENTS AND PHOSPHATE SUBSTITUTES
DE3412188A1 (en) * 1984-04-02 1985-10-10 Henkel KGaA, 4000 Düsseldorf LAUNDRY DETERGENT
DE3444311A1 (en) * 1984-12-05 1986-06-05 Degussa Ag, 6000 Frankfurt AQUEOUS, STABLE SUSPENSION OF WATER-INSOLUBLE SILICATES CAPABLE OF CALCIUMIONS AND THE USE THEREOF FOR THE PRODUCTION OF DETERGENT AND CLEANING AGENTS
JPS63177495A (en) * 1987-01-16 1988-07-21 Sharp Corp Semiconductor laser device
US5174918A (en) * 1987-06-06 1992-12-29 Degussa Ag Stable aqueous suspensions of detergent zeolites and four oxo-alcohol ethoxylates
KR101311020B1 (en) * 2008-11-07 2013-09-25 에프. 호프만-라 로슈 아게 Fine-grained filler substances for photometric reaction films

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2412837A1 (en) * 1973-04-13 1974-10-31 Henkel & Cie Gmbh PROCESS FOR WASHING AND CLEANING THE SURFACES OF SOLID MATERIALS, IN PARTICULAR TEXTILES, AND MEANS FOR CARRYING OUT THE PROCESS
DE2544019A1 (en) * 1974-10-04 1976-04-08 Henkel & Cie Gmbh METHOD OF WASHING TEXTILES, AND MEANS OF CARRYING OUT THE METHOD
DE2615698A1 (en) * 1976-04-09 1977-10-20 Henkel & Cie Gmbh Stable, pumpable, water-insoluble silicate suspension - contg. dispersant and auxiliary stabilising, non-surfactant, water-soluble salt
EP0016344A1 (en) * 1979-02-23 1980-10-01 BASF Aktiengesellschaft Process for producing storage-stable and free-flowing suspensions of aluminium silicate which can be pumped, by wet crushing

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4083793A (en) * 1973-05-23 1978-04-11 Henkel Kommanditgesellschaft Auf Aktien Washing compositions containing aluminosilicates and nonionics and method of washing textiles
AT336153B (en) * 1974-10-08 1977-04-25 Henkel & Cie Gmbh AQUATIC DETERGENT FOR CLEANING TEXTILE FLAT COVERINGS
US4169075A (en) * 1974-10-10 1979-09-25 Henkel Kommanditgesellschaft Auf Aktien Process for the production of powdery washing agents by spray-drying
DE2517218B2 (en) * 1975-04-18 1977-05-05 Henkel & Cie GmbH, 4000 Düsseldorf; Deutsche Gold- und Silber-Scheideanstalt vormals Roessler, 6000 Frankfurt TYPE A CRYSTALLINE ZEOLITE POWDER
AT362481B (en) * 1976-02-06 1981-05-25 Henkel Kgaa STABLE, PUMPABLE, SUITABLE AS A STORAGE SUSPENSION, AQUEOUS SUSPENSION OF WATER-INSOLUBLE SILICATES THAT TAKE CALCIUM
US4409136A (en) * 1977-01-31 1983-10-11 Colgate Palmolive Company Molecular sieve zeolite-built detergent paste
BE874420A (en) * 1978-03-02 1979-08-23 Unilever Nv PROCESS FOR THE PRODUCTION OF DETERGENT COMPOSITIONS
DE2856087A1 (en) * 1978-12-23 1980-07-10 Henkel Kgaa Powdered washing compsn. contg. aluminosilicate and brightener - with nonionic polyglycol ether added before drying to inhibit discolouration

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2412837A1 (en) * 1973-04-13 1974-10-31 Henkel & Cie Gmbh PROCESS FOR WASHING AND CLEANING THE SURFACES OF SOLID MATERIALS, IN PARTICULAR TEXTILES, AND MEANS FOR CARRYING OUT THE PROCESS
DE2544019A1 (en) * 1974-10-04 1976-04-08 Henkel & Cie Gmbh METHOD OF WASHING TEXTILES, AND MEANS OF CARRYING OUT THE METHOD
DE2615698A1 (en) * 1976-04-09 1977-10-20 Henkel & Cie Gmbh Stable, pumpable, water-insoluble silicate suspension - contg. dispersant and auxiliary stabilising, non-surfactant, water-soluble salt
EP0016344A1 (en) * 1979-02-23 1980-10-01 BASF Aktiengesellschaft Process for producing storage-stable and free-flowing suspensions of aluminium silicate which can be pumped, by wet crushing

Also Published As

Publication number Publication date
BR8301254A (en) 1983-11-22
ATE20537T1 (en) 1986-07-15
CA1200456A (en) 1986-02-11
DK56983D0 (en) 1983-02-10
DK158520B (en) 1990-05-28
ES520187A0 (en) 1985-06-16
NO830511L (en) 1983-09-19
KR840004158A (en) 1984-10-10
EP0088866B1 (en) 1986-06-25
FI830493A0 (en) 1983-02-14
DE3209631C2 (en) 1988-02-25
SU1443805A3 (en) 1988-12-07
DK56983A (en) 1983-09-18
DE3209631A1 (en) 1983-09-29
ES8505832A1 (en) 1985-06-16
KR910001604B1 (en) 1991-03-16
US4486331A (en) 1984-12-04
JPH0357959B2 (en) 1991-09-03
JPS58168698A (en) 1983-10-05
FI830493L (en) 1983-09-18
DK158520C (en) 1990-10-29
DE3364223D1 (en) 1986-07-31

Similar Documents

Publication Publication Date Title
DE2527388C3 (en) Use of stable suspensions of water-insoluble silicates capable of binding calcium ions for the production of detergents and cleaners
EP0016344B1 (en) Process for producing storage-stable and free-flowing suspensions of aluminium silicate which can be pumped, by wet crushing
EP0185660B1 (en) Stabilized aqueous zeolite suspension
EP0183945B1 (en) Aqueous stable suspensions of water-insoluble silicates, capable of binding calcium ions, and their use for the production of washing and cleaning agents
EP0195127B1 (en) Detergent builder
DE2727475C2 (en) Process for the production of surfactant-containing, cation-exchanging aluminosilicates
EP0088866B1 (en) Aqueous stable suspensions of water-insoluble silicates capable of binding calciumions, and their use in the production of washing and cleaning agents
EP0279040B1 (en) Builder for washing agents
DE2501698C2 (en) Mixtures containing optical brighteners and processes for their preparation
EP0144492B1 (en) Aqueuos stable suspension of water insoluble silicates and their use for the production of phosphate-substitutes for washsing and cleaning agents
EP0294694B1 (en) Aquoeus stable suspensions of water insoluble silicates capable of binding calciumions, and their use in the production of washing and cleaning compositions
EP0191187B1 (en) Detergent builder
EP0504564B1 (en) Aqueous, stable suspensions of water insoluble silicates which are able to bind calcium ions and their use in the production of washing and cleaning agents
EP0294574A2 (en) Aqueous stable suspensions of water insoluble silicates capable of binding calcium ions, and their use in the production of washing and cleaning compositions
EP0279038B1 (en) Builder for washing agents
DE3818657A1 (en) Stable aqueous suspension of silicates which are insoluble in water and capable of binding calcium ions, and the use thereof for producing detergents and cleaners
EP0279039B1 (en) Builder for washing agents
EP0249163B1 (en) Detergents containing granular, agglomerated sodium metasilicate, process for their preparation and their use
EP0046171A1 (en) Storable and flowable aqueous suspensions of sodium aluminosilicates
AT330102B (en) PROCESS FOR THE PRODUCTION OF NEW, RONT-GENERAL AMORPHERIC, CATION-EXCHANGING ALUMINUM SILICATES, WHICH MAY CONTAIN BONDED WATER
DEB0026892MA (en)

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

17P Request for examination filed

Effective date: 19830120

AK Designated contracting states

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

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: 20537

Country of ref document: AT

Date of ref document: 19860715

Kind code of ref document: T

ITF It: translation for a ep patent filed
REF Corresponds to:

Ref document number: 3364223

Country of ref document: DE

Date of ref document: 19860731

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19890131

Year of fee payment: 9

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

Ref country code: DE

Payment date: 19901217

Year of fee payment: 9

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

Ref country code: SE

Payment date: 19901218

Year of fee payment: 9

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

Ref country code: AT

Payment date: 19910102

Year of fee payment: 9

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

Ref country code: GB

Payment date: 19910111

Year of fee payment: 9

Ref country code: CH

Payment date: 19910111

Year of fee payment: 9

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

Ref country code: FR

Payment date: 19910123

Year of fee payment: 9

ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19911224

Year of fee payment: 10

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

Ref country code: GB

Effective date: 19920120

Ref country code: AT

Effective date: 19920120

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

Ref country code: SE

Effective date: 19920121

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

Ref country code: LI

Effective date: 19920131

Ref country code: CH

Effective date: 19920131

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

Ref country code: NL

Effective date: 19920801

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
REG Reference to a national code

Ref country code: GB

Ref legal event code: PCNP

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

Ref country code: FR

Effective date: 19920930

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: 19921001

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

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

Ref country code: BE

Effective date: 19930131

BERE Be: lapsed

Owner name: DEGUSSA A.G.

Effective date: 19930131

EUG Se: european patent has lapsed

Ref document number: 83100470.0

Effective date: 19920806