EP0279038B1 - Builder for washing agents - Google Patents

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Publication number
EP0279038B1
EP0279038B1 EP87117460A EP87117460A EP0279038B1 EP 0279038 B1 EP0279038 B1 EP 0279038B1 EP 87117460 A EP87117460 A EP 87117460A EP 87117460 A EP87117460 A EP 87117460A EP 0279038 B1 EP0279038 B1 EP 0279038B1
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Prior art keywords
zeolite
water
der
calcium
weight
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German (de)
French (fr)
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EP0279038A1 (en
Inventor
Manfred Dr. Diehl
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Evonik Operations GmbH
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Degussa GmbH
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    • 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
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC

Definitions

  • Powdered zeolite type A which can be used as a phosphate substitute in detergents, is a lumpy powder which tends to agglomerate due to its small particle size. It is difficult to mix this zeolite powder with the other detergent components to form a homogeneous powder. The fact that the finished mixture tends to segregate again makes it difficult.
  • zeolite granules are added to the already spray-dried detergent components. These zeolite granules are u. a. produced by spray drying an aqueous suspension of the zeolite powder with the addition of further detergent components.
  • An aluminum silicate can preferably be used as the component according to formula 1.
  • y can be a number from 1.3 to 4.
  • the crystalline component according to the formula can be a type A zeolite.
  • the aluminum silicates according to the formula can be naturally occurring or else synthetically produced products, only synthetically produced products being used in the present invention.
  • the production can e.g. B. 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 both components in the solid state in the presence of water.
  • Aluminum silicates can also be produced from Al (OH) 2 , A1 2 0 3 or SiO 2 by reaction with alkali silicate or alkali aluminate solutions.
  • the production can also be carried out by other known processes.
  • the invention relates to aluminum silicates which have a three-dimensional space lattice structure.
  • This molecular formula comprises two types of different crystal structures (or their non-crystalline precursors), which also differ in their molecular formulas. They are:
  • the crystalline aluminum silicate present in aqueous suspension can be separated from the remaining aqueous solution by filtration and dried. Depending on the drying conditions, the product contains more or less bound water.
  • the aluminum silicates do not need to be dried at all after their preparation in order to prepare the detergent builders according to the invention; rather, an aluminum silicate that is still moist from manufacture can be used, and this is particularly advantageous.
  • the particle size of the individual aluminum saucer particles can be different and e.g. B. are in the range between 0.1 microns and 0.1 mm. This refers to the primary particle size, i.e. H. 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 ⁇ m, in particular 8 to 0.1 ⁇ m.
  • These aluminum silicates preferably no longer contain primary or secondary particles with diameters above 45 ⁇ m.
  • Secondary particles are particles that are caused by agglomeration of the primary particles have formed into larger structures.
  • the use of the aluminum silicates which are still moist from their production for the production of the detergent builders 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 2517 218, DE-OS 26 52 419, DE-OS 26 51420, DE-OS 26 51436, DE-OS 26 51 437, DE-OS 26 51 445 or DE-OS 26 51 485 can be 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.
  • Addition products of 4 to 40, preferably 4 to 20 moles of ethylene oxide with 1 mole of fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide can be used as nonionic surfactants.
  • the addition products of 5-16 mol of ethylene oxide with coconut or tallow fatty alcohols, with oleyl alcohol or with secondary alcohols with 8-18, preferably 12-18 C atoms, and with mono- or dialkylphenols with 6-14 C atoms in the are particularly important Alkyl residues.
  • the adduct of 5 moles of ethylene oxide with tallow fatty alcohol is of particular interest.
  • non-or not completely water-soluble polyglycol ethers with 1-4 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants.
  • non-ionic surfactants which can be used are the water-soluble addition products of 20-250 ethylene glycol ether groups and 10-100 propylene glycol ether groups of ethylene oxide onto polypropylene glycol, alkylenediamine polypropylene glycol and alkylpolypropylene glycols with 1-10 C atoms in the alkyl chain, in which the polypropylene glycol chain acts as a hydrophobic glycol chain
  • Nonionic surfactants of the amine oxide or sulfoxide type can also be used.
  • the alkylphenol ethoxylates and the isotridecyl alcohol ethoxylates can each 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 proportion of carboxymethyl cellulose and / or methyl cellulose can be 2.4 to 5.0% by weight in a preferred embodiment of the invention.
  • NaOH and / or KOH can be used as alkali.
  • the granular detergent builder according to the invention can be prepared by mixing the individual components with one another, setting a consistency suitable for spray drying by measuring the amount of water and spray-drying the suspension thus obtained by known methods.
  • the granulated detergent builder according to the invention is stable in transportation, easy to redisperse and extremely low dust.
  • the product according to the invention has an extremely high absorption capacity for water and surfactants.
  • the granular detergent builder according to the invention can be processed into a detergent simply by mixing it with the other granular detergent constituents. The mixture does not separate.
  • a zeolite A filter cake according to DE-OS 26 51 485 is produced.
  • the powdery zeolite of type A obtained in this way has the particle spectrum given there.
  • the zeolite A filter cake is stirred up with a dissolver and then heated to 45 ° C. in a 50 l vessel.
  • the nonionic surfactant is stirred in at 75-76 rpm with a MIG stirrer 15 ', the temperature of the slurry rising to 50 ° C.
  • the funding tests were carried out on a power tube conveyor screw. The samples were subjected to one or two conveyance. See Table 2 for results.
  • test products 1 and 2 have the best stability despite the very coarse grain. These two samples show only a slight deterioration in the flow behavior in the bulk cone, even after being pumped twice, and are therefore to be assessed better than the comparison sample 3 according to the prior art.
  • Both of the detergent builders according to the invention show an improvement in the powder properties, ie a higher conveying stability and a coarser grain.
  • the immersion depth is kept constant by a brass disc (diameter: 15 cm, thickness: 1 mm) soldered to the outer wall of the filler pipe.
  • the frequency of the shaking trough should be 50 Hz and the opening gap should be set so that the substance has passed through the shaking trough in 1 minute.
  • the powder falls through a funnel (3) and a filler pipe (4) into the inner cylinder of the test apparatus (5) below, while the dust outside this vessel accumulates on the base plate (6) of the outer cylinder (7).
  • any remaining powder in the funnel is transferred into the apparatus by gently tapping the funnel.
  • the dust deposited on the polished floor plate is collected in a small bowl with a metal spatula and weighed out.
  • the dust content is given in percent based on the weight.

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  • 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)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

Granular detergent builders comprise 70-80 wt.% finely divided zeolite, 2-3 wt.% nonionic surfactant, 0.5-5 wt.% carboxymethyl cellulose and/or methyl cellulose, 0-1 wt.% alkali, balance H2O. The zeolite is of formula (Q2/nO)x.M2O3.(SiO2/y, where Q is an n-valent cation exchangeable with Ca; x = 0.7-1.5; Me = Al or B; y = 0.8-6. Pref. the zeolite is powdered zeolite A with the particle size distribution described in DE2651485. The surfactant is an ethoxylated fatty alcohol or alkylphenol.

Description

Pulverförmiger Zeolith des Typs A, der als Phosphatsubstitut in Waschmitteln eingesetzt werden kann, stellt aufgrund seiner kleinen Teilchengröße ein klumpiges, zur Agglomeration neigendes Pulver dar. Es ist schwierig, dieses Zeolithpulver mit den übrigen Waschmittelbestandteilen zu einem homogenen Pulver zu vermischen. Erschwerend wirkt, daß das fertige Gemisch wieder zum Entmischen neigt.Powdered zeolite type A, which can be used as a phosphate substitute in detergents, is a lumpy powder which tends to agglomerate due to its small particle size. It is difficult to mix this zeolite powder with the other detergent components to form a homogeneous powder. The fact that the finished mixture tends to segregate again makes it difficult.

Um dieses Mischproblem zu vermeiden, werden den bereits sprühgetrockneten Waschmittelkomponenten Zeolithgranulate zugesetzt. Diese Zeolithgranulate werden u. a. durch Sprühtrocknen einer wässrigen Suspension des Zeolithpulvers unter Zusatz von weiteren Waschmittelbestandteilen hergestellt.In order to avoid this mixing problem, zeolite granules are added to the already spray-dried detergent components. These zeolite granules are u. a. produced by spray drying an aqueous suspension of the zeolite powder with the addition of further detergent components.

Es ist bekannt, Zeolithsuspensionen mit Natriumsulfat zu versetzen, zu Zeolithgranulaten sprühzutrocknen und den übrigen Waschmittelbestandteilen zuzumischen (vgl. EP-OS 870, Kali-Chemie). Diese bekannten Zeolithgranulate haben den Nachteil, daß sie nicht die an sie gestellten Anforderungen erfüllen. So ist es notwendig, daß das Zeolithgranulat ein unvermindertes Calciumbindevermögen, eine gute Redispergierbarkeit und eine gute Transport- und Kornstabilität aufweist. Von besonderem Belang ist ein möglichst niedriger Staubgehalt.It is known to add zeolite suspensions with sodium sulfate, to spray-dry to zeolite granules and to add the other detergent components (cf. EP-OS 870, Kali-Chemie). These known zeolite granules have the disadvantage that they do not meet the requirements placed on them. So it is necessary that the zeolite granules have an undiminished calcium binding capacity, good redispersibility and good transport and grain stability. The lowest possible dust content is of particular concern.

Es ist weiterhin bekannt, granulierte Waschmittelbuilder, bestehend aus :

  • 70 bis 80 Gew.-% eines wasserunlösliche, zum Binden von Calcium befähigten Silikates in Form einer feinverteilten, gebundenes Wasser enthaltenden, synthetisch hergestellten, wasserunlöslichen, kristallinen Verbindung der allgemeinen Formel
    Figure imgb0001
    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,
    Figure imgb0002
    zur Herstellung von phosphatfreien Waschmitteln zu verwenden (DE-OS 35 04 450).
It is also known granular detergent builder consisting of:
  • 70 to 80 wt .-% of a water-insoluble, capable of binding calcium in the form of a finely divided, bound water-containing, synthetically produced, water-insoluble, crystalline compound of the general formula
    Figure imgb0001
     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,
    Figure imgb0002
    to be used for the production of phosphate-free detergents (DE-OS 35 04 450).

Aus der EP-A 0 191 187 ist ein granulierter Waschmittelbuilder bekannt. Er besteht aus:

  • 65 bis 80 Gew.-% eines wasserunlöslichen, zum Binden von Calcium befähigten in Form einerfeinverteilten, gebundenes Wasser enthaltenden, synthetisch hergestellten, wasserunlöslichen, kristallinen Verbindung der allgemeinen Formel (Kat2/nO)x · Me203 - (SiO2)y, (1) 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,
    Figure imgb0003
    Dieser granulierte Waschmittelbuilder kann zur Herstellung von phosphatfreien Waschmitteln eingesetzt werden.
A granulated detergent builder is known from EP-A 0 191 187. It consists of:
  • 65 to 80% by weight of a water-insoluble, capable of binding calcium in the form of a finely divided, bound water-containing, synthetically produced, water-insoluble, crystalline compound of the general formula (Kat 2 / n O) x · Me 2 0 3 - (SiO 2 ) y , (1) in the cat is 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,
    Figure imgb0003
    This granulated detergent builder can be used to produce phosphate-free detergents.

Gegenstand der Erfindung ist ein granulierter Waschmittelbuilder, bestehend aus :

  • 70 bis 80 Gew.-% eines wasserunlöslichen, zum Binden von Calcium befähigten Silikates in Form einer feinverteilten, gebundenes Wasser enthaltenden, synthetisch hergestellten, wasserunlöslichen, kristallinen Verbindung der allgemeinen Formel
    Figure imgb0004
    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
    Figure imgb0005
    In dem erfindungsgemäßen Waschmittelbuilder kann die Komponente gemäß der Formel kristallin sein.
The invention relates to a granulated detergent builder consisting of:
  • 70 to 80 wt .-% of a water-insoluble, capable of binding calcium silicate in the form of a finely divided, bound water-containing, synthetically produced, water-insoluble, crystalline compound of the general formula
    Figure imgb0004
     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
    Figure imgb0005
    In the detergent builder according to the invention, the component according to the formula can be crystalline.

Bevorzugterweise kann als Komponente gemäß der Formel 1 ein Aluminiumsilikat eingesetzt werden.An aluminum silicate can preferably be used as the component according to formula 1.

In der Formel kann y eine Zahl von 1,3 bis 4 bedeuten.In the formula, y can be a number from 1.3 to 4.

Die kristalline Komponente gemäß der Formel kann in einer bevorzugten Ausführungsform ein Zeolith des Typs A sein.In a preferred embodiment, the crystalline component according to the formula can be a type A zeolite.

Die Aluminiumsilikate gemäß der Formel können natürlich vorkommende oder aber synthetisch hergestellte Produkte sein, wobei in der vorliegenden Erfindung nur synthetisch hergestellten Produkte eingesetzt werden. 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 Komponenten erhält man bei Anwesenheit von Wasser die gewünschten Aluminiumsilikate. Auch aus AI(OH)2, A1203 oder SiO2lassen sich durch Umsetzen mit Alkalisilikat- bzw. Alkalialuminat-Lösungen 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 according to the formula can be naturally occurring or else synthetically produced products, only synthetically produced products being used in the present invention. The production can e.g. B. 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 both components in the solid state in the presence of water. Aluminum silicates can also be produced from Al (OH) 2 , A1 2 0 3 or SiO 2 by reaction with alkali silicate or alkali aluminate solutions. The production can also be carried out by other known processes. In particular, 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 imgb0006
Diese Summenformel umfaßt zwei Typen verschiedener Kristallstrukturen (bzw. deren nicht kristalline Vorprodukte), die sich auch durch ihre Summenformeln unterscheiden. Es sind dies :
Figure imgb0007
 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 imgb0006
 This molecular formula comprises two types of different crystal structures (or their non-crystalline precursors), which also differ in their molecular formulas. They are:
Figure imgb0007

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

Das in wässriger Suspension vorliegende kristalline Aluminiumsilikat läßt sich durch Filtration von der verbleibenden wässrigen Lösung abtrennen und trocknen. Je nach den Trocknungsbedingungen enthält das Produkt mehr oder weniger gebundenes Wasser. Die Aluminiumsilikate brauchen jedoch nach ihrer Herstellung zur Bereitung der erfindungsgemäßen Waschmittelbuilder überhaupt nicht getrocknet zu werden ; vielmehr kann - und dies ist besonders vorteilhaft - eine von der Herstellung noch feuchtes Aluminiumsilikat verwendet werden.The crystalline aluminum silicate present in aqueous suspension can be separated from the remaining aqueous solution by filtration and dried. Depending on the drying conditions, the product contains more or less bound water. However, the aluminum silicates do not need to be dried at all after their preparation in order to prepare the detergent builders according to the invention; rather, an aluminum silicate that is still moist from manufacture can be used, and this is particularly advantageous.

Die Teilchengröße der einzelnen Aluminiumsükatpartikel kann verschieden sein und z. B. im Bereich zwischen 0,1 µm 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 µm, insbesondere von 8 bis 0,1 µm bestehen.The particle size of the individual aluminum saucer particles can be different and e.g. B. are in the range between 0.1 microns and 0.1 mm. This refers to the primary particle size, i.e. H. 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 µm, in particular 8 to 0.1 µm.

Vorzugsweise enthalten diese Aluminiumsilikate keine Primär- bzw. Sekundärteilchen mehr mit Durchmessern oberhalb von 45 µm. 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 μm. Secondary particles are particles that are caused by agglomeration of the primary particles have formed into larger structures.

Im Hinblick auf die Agglomeration der Primärteilchen zu größeren Gebilden hat sich die Verwendung der von ihrer Herstellung noch feuchten Aluminiumsilikate zur Herstellung der erfindungsgemäßen Waschmittelbuilder 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 production for the production of the detergent builders 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 2517 218, DE-OS 26 52 419, DE-OS 26 51420, DE-OS 26 51436, DE-OS 26 51 437, DE-OS 26 51 445 oder 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 2517 218, DE-OS 26 52 419, DE-OS 26 51420, DE-OS 26 51436, DE-OS 26 51 437, DE-OS 26 51 445 or DE-OS 26 51 485 can be 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.

Als nichtionische Tenside sind Anlagerungsprodukte von 4 bis 40, vorzugsweise 4 bis 20 Mol Äthylenoxid an 1 Mol Fettalkohol, Alkylphenol, Fettsäure, Fettamin, Fettsäureamid oder Alkansulfonamid verwendbar. Besonders wichtig sind die Anlagerungsprodukte von 5-16 Mol Äthylenoxid an Kokos oder Talgfettalkohole, an Oleylalkohol oder an sekundäre Alkohole mit 8-18, vorzugsweise 12-18 C-Atomen, sowie an Mono- oder Dialkylphenole mit 6-14 C-Atomen in den Alkylresten. Von besonderem Interesse ist das Anlagerungsprodukt von 5 Mol Äthylenoxid an Talgfettalkohol. Neben diesen wasserlöslichen nichtionischen Tensiden sind aber auch nicht bzw. nicht vollständig wasserlösliche Polyglykoläther mit 1-4 Äthylenglykolätherresten im Molekül von Interesse, insbesondere wenn sie zusammen mit wasserlöslichen nichtionischen oder anionischen Tensiden eingesetzt werden.Addition products of 4 to 40, preferably 4 to 20 moles of ethylene oxide with 1 mole of fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide can be used as nonionic surfactants. The addition products of 5-16 mol of ethylene oxide with coconut or tallow fatty alcohols, with oleyl alcohol or with secondary alcohols with 8-18, preferably 12-18 C atoms, and with mono- or dialkylphenols with 6-14 C atoms in the are particularly important Alkyl residues. The adduct of 5 moles of ethylene oxide with tallow fatty alcohol is of particular interest. In addition to these water-soluble nonionic surfactants, non-or not completely water-soluble polyglycol ethers with 1-4 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants.

Weiterhin sind als nichtionische Tenside die wasserlöslichen, 20-250 Äthylenglykoläthergruppen und 10-100 Propylenglykoläthergruppen enthaltenden Anlagerungsprodukte von Äthylenoxid an Polypropylenglykol, Alkylendiaminpolypropylenglykol und Alkylpolypropylenglykole mit 1-10 C-Atomen in der Alkylkette brauchbar, in denen die Polypropylenglykolkette als hydrophober Rest fungiertFurthermore, the non-ionic surfactants which can be used are the water-soluble addition products of 20-250 ethylene glycol ether groups and 10-100 propylene glycol ether groups of ethylene oxide onto polypropylene glycol, alkylenediamine polypropylene glycol and alkylpolypropylene glycols with 1-10 C atoms in the alkyl chain, in which the polypropylene glycol chain acts as a hydrophobic glycol chain

Auch nichtionische Tenside vom Typ der Aminoxide oder Sulfoxide sind verwendbar.Nonionic surfactants of the amine oxide or sulfoxide type can also be used.

Von besonderem Interesse ist für die Verwendung als nichtionisches Tensid ein Gemisch mindestens zweier unterschiedlicher Fettalkoholethoxylate auf Basis Isotridecylalkohol oder einem aliphatischen C13-Alkohol und Ethylenoxid. Dieses Gemisch kann bevorzugterweise aus Fettalkoholethoxylaten mit 4,5 bis 5,5 EO und Fettalkoholethoxylaten mit 6 bis 8 EO bestehen. Weiterhin kann als nichtionisches Tensid eine Mischung von mindestens zwei verschiedenen Alkylphenoläthoxylaten der Formel

Figure imgb0008
verwendet werden.

  • R kann dabei ein aliphatische Rest mit 1 bis 15, beispielsweise-CH3, -C2H5, Propyl, Butyl, Pentyl, Hexyl- , Heptil-, Octyl- und Nonyl vorzugsweise mit 9 C-Atomen wie Nonyl sein. Der Rest R kann in ortho, meta oder/und para-Stellung substitutiert sein. Es können auch Gemische eingesetzt werden, in denen neben p-substituiertem Arylring auch o-substitutierter Benzolring vorhanden ist Es werden Gemische eingesetzt, in denen zu 90% eine p-Substitution und zu 10% eine ortho-Substitution vorliegt.
  • 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 bedeuter. n kann aber auch bei Gemischen der Alkylphenolate jeweils 7 oder 9 oder 12 bedeuten.
Of particular interest for use as a nonionic surfactant is a mixture of at least two different fatty alcohol ethoxylates based on isotridecyl alcohol or an aliphatic C 13 alcohol and ethylene oxide. This mixture can preferably consist of fatty alcohol ethoxylates with 4.5 to 5.5 EO and fatty alcohol ethoxylates with 6 to 8 EO. A mixture of at least two different alkylphenol ethoxylates of the formula can also be used as the nonionic surfactant
Figure imgb0008
 be used.
  • R can be an aliphatic radical with 1 to 15, for example -CH 3 , -C 2 H 5 , propyl, butyl, pentyl, hexyl, heptile, octyl and nonyl, preferably with 9 carbon atoms such as nonyl. The radical R can be substituted in the ortho, meta and / or para position. Mixtures can also be used in which, in addition to p-substituted aryl ring, also o-substituted benzene ring is present. Mixtures are used in which 90% is p-substitution and 10% is ortho-substitution.
  • n may be 2 to 7, preferably 4 to 6, in particular 5 and in the other alkylphenol ethoxylate 8 to 15, preferably 8 to 12, in particular 9 or 10, more important in the alkylphenol ethoxylate used in the mixture. However, n can also mean 7 or 9 or 12 in the case of mixtures of the alkylphenolates.

Die Alkylphenoläthoxylate und die Isotridecylalkoholethoxylate können jeweils 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 der Formel, in derR=Nonyl und n = 5 bzw. 9 bedeuten.The alkylphenol ethoxylates and the isotridecyl alcohol ethoxylates can each 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 to the formula in which R = nonyl and n = 5 and 9 respectively.

Der Anteil an Carboxymethylcellulose und/oder Methylcellulose kann in einer bevorzugten Ausführungsform der Erfindung 2,4 bis 5,0 Gew.-% betragen.The proportion of carboxymethyl cellulose and / or methyl cellulose can be 2.4 to 5.0% by weight in a preferred embodiment of the invention.

Als Alkali können NaOH und/oder KOH eingesetzt werden. Die Herstellung des erfindungsgemäßen granulatförmigen Waschmittelbuilders kann erfolgen, in dem man die einzelnen Komponenten miteinander vermischt, eine für eine Sprühtrocknung geeignete Konsistenz durch Bemessung der Wassermenge einstellt und die so erhaltene Suspension nach bekannten Verfahren sprühtrocknet.NaOH and / or KOH can be used as alkali. The granular detergent builder according to the invention can be prepared by mixing the individual components with one another, setting a consistency suitable for spray drying by measuring the amount of water and spray-drying the suspension thus obtained by known methods.

Der erfindungsgemäße, granulierte Waschmittelbuilder ist transportstabil, gut redispergierbar und extrem staubarm.The granulated detergent builder according to the invention is stable in transportation, easy to redisperse and extremely low dust.

Weiterhin weist das erfindungsgemäße Produkt ein extrem hohes Absorptionsvermögen für Wasser und Tenside auf.Furthermore, the product according to the invention has an extremely high absorption capacity for water and surfactants.

Der erfindungsgemäße granulierte Waschmittelbuilder kann aufgrund seiner körnigen Erscheinungsform durch einfaches Vermischen mit den anderen körnigen Waschmittelbestandteilchen zu einem Waschmittel verarbeitet werden. Eine Entmischung des Gemisches findet nicht statt.Because of its granular appearance, the granular detergent builder according to the invention can be processed into a detergent simply by mixing it with the other granular detergent constituents. The mixture does not separate.

BeispieleExamples

Es wird ein Zeolith-A-Filterkuchen gemäß DE-OS 26 51 485 hergestellt. Der dabei erhaltene pulverförmige Zeolith des Typs A weist das dort angegebene Teilchenspektrum auf. Der Zeolith-A-Filterkuchen wird mit einem Dissolver aufgerührt und anschließend in einem 50 I Gefäß auf 45°C temperiert. Dort wird das nichtionische Tensid mit 75-76 U/min mit einem MIG-Rührer 15' eingerührt, wobei die Temperatur des Slurries auf 50°C ansteigt.A zeolite A filter cake according to DE-OS 26 51 485 is produced. The powdery zeolite of type A obtained in this way has the particle spectrum given there. The zeolite A filter cake is stirred up with a dissolver and then heated to 45 ° C. in a 50 l vessel. There, the nonionic surfactant is stirred in at 75-76 rpm with a MIG stirrer 15 ', the temperature of the slurry rising to 50 ° C.

Es wird das folgende Tensid als einzige Komponente oder in Mischungen als Stabilisator eingesetzt :

  • Talgalkoholethoxylat 5 EO

Die erhaltene Suspension wird mit den übrigen in den Tabellen aufgeführten Bestandteilen vermischt und anschließend sprühgetrocknet (Düsentrockner Eingangstemperatur 180°C, Ablufttemperatur 75°C).The following surfactant is used as the only component or in mixtures as a stabilizer:
  • Tallow alcohol ethoxylate 5 EO

The suspension obtained is mixed with the other constituents listed in the tables and then spray-dried (nozzle dryer inlet temperature 180 ° C., exhaust air temperature 75 ° C.).

Die Förderversuche wurden auf einer Kraft-Rohrförderschnecke durchgeführt. Die Proben wurden einer ein- bzw. zweimaligen Förderung unterworfen. Ergebnisse siehe Tabelle 2.The funding tests were carried out on a power tube conveyor screw. The samples were subjected to one or two conveyance. See Table 2 for results.

Die mittlere Teilchengröße der ungeförderten und der geförderten Compound-Muster ist Tabelle 3 zu entnehmen.The mean particle size of the unsupported and the promoted compound samples is shown in Table 3.

Die Untersuchung der verschiedenen erfindungsgemäßen Waschmittelbuilder vor und nach der Förderung hat gezeigt, daß die Versuchsprodukte 1 und 2 trotz recht grobem Korn die beste Stabilität aufweisen. Diese zwei Muster zeigen im Schüttkegel selbst nach zweimaliger Förderung nur eine geringfügige Verschlechterung des Fließverhaltens und sind damit besser als das Vergleichsmuster 3 nach dem Stand der Technik zu beurteilen.The examination of the various detergent builders according to the invention before and after the conveying has shown that the test products 1 and 2 have the best stability despite the very coarse grain. These two samples show only a slight deterioration in the flow behavior in the bulk cone, even after being pumped twice, and are therefore to be assessed better than the comparison sample 3 according to the prior art.

Die Vorteile dieser neuen Produkte mit erhöhtem CMC-Gehalt werden bereits im ungeförderten Zustand anhand des sehr geringen Staubanteils (0,03 - 0,06%) und der hervorragenden Schüttkegelhöhe von nur 14 mm deutlich.The advantages of these new products with increased CMC content are already evident in the unsupported state due to the very low dust content (0.03 - 0.06%) and the excellent pouring cone height of only 14 mm.

Die Fließfähigkeit, bestimmt mit den Glaskonusgefäßen, erhielt deshalb "nur" Note 2, weil das grobe Korn der neuen Produkte durch die öffnung im Glaskonus 1 nicht durchlief.The flowability, determined with the glass cone tubes, was "only" given a grade 2 because the coarse grain of the new products did not flow through the opening in the glass cone 1.

Alle beide erfindungsgemäßen Waschmittelbuilderzeigen eine Verbesserung in den Pulvereigenschaften, d. h. eine höhere Förderstabilität und ein gröberes Korn.

Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
 Both of the detergent builders according to the invention show an improvement in the powder properties, ie a higher conveying stability and a coarser grain.
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012

Der Staubtest nach Dr. Groschopp wird wie folgt durchgeführt :

  • Das über eine Schüttelrinne in einen Zylinderfallende Pulver wird in einem unter der Schüttelstelle stehenden Gefäß aufgefangen, während sich die Staubanteile außerhalb dieses Gefäßes auf der Bodenplatte des Zylinders absetzen und gravimetrisch bestimmt werden können. Dabei werden die folgenden Geräte verwendet:
The dust test according to Dr. Groschopp is carried out as follows:
  • The powder falling into a cylinder via a shaking channel is collected in a vessel under the shaking point, while the dust particles outside this vessel settle on the base plate of the cylinder and can be determined gravimetrically. The following devices are used:

Apparatur zur Bestimmung des Staubes, bestehend aus Schüttelrinne

  • Hersteller: AEG, Typ DR 50
  • 220 V 50 Hz, 0,15 A.
Apparatus for determining the dust, consisting of a shaking channel
  • Manufacturer: AEG, type DR 50
  • 220 V 50 Hz, 0.15 A.

Außenzylinder

  • Höhe: 70 cm, Durchmesser 40 cm
  • oben geschlossen, unten offen

Die Deckplatte ist in der Mitte mit einer kreisförmigen Öffnung (Durchmesser: 3 cm) zur Aufnahme des Einfüllrohres versehen.Outer cylinder
  • Height: 70 cm, diameter 40 cm
  • closed at the top, open at the bottom

The cover plate is provided in the middle with a circular opening (diameter: 3 cm) for receiving the filler pipe.

Innenzylinder

  • Höhe : 10 cm, Durchmesser: 18 cm
  • unten geschlossen, oben offen.
Inner cylinder
  • Height: 10 cm, diameter: 18 cm
  • closed at the bottom, open at the top.

Bodenplatte

  • Form: Rund
  • Durchmesser: 48 cm
  • Einfüllrohr
  • Länge: 30 cm, Durchmesser: 2,5 cm
  • Eintauchtiefe des Rohres in den Außenzylinder : 20 cm.
Base plate
  • Shape: round
  • Diameter: 48 cm
  • Filler pipe
  • Length: 30 cm, diameter: 2.5 cm
  • Immersion depth of the tube in the outer cylinder: 20 cm.

Die Eintauchtiefe wird durch ein auf die Außenwand des Einfüllrohres gelötete Messingscheibe (Durchmesser : 15 cm, Stärke : 1 mm) konstant gehalten.The immersion depth is kept constant by a brass disc (diameter: 15 cm, thickness: 1 mm) soldered to the outer wall of the filler pipe.

Trichter

  • oberer Durchmesser: 15 cm
  • Durchmesser des Auslaufs : 1,8 cm
  • Länge des Trichterrohres : 8 cm

Die Apparatur wird in der Zeichnung dargestellt. Gemäß Figur wird die Schüttelrinne auf einem Labortisch aufgestellt. Die Anordnung der restlichen Apparatur soll derart erfolgen, daß der Auslauf der Schüttelrinne direkt über der Mitte des Trichters (3) liegt und sein Abstand von der Oberkante des Trichters 5,5 cm beträgtfunnel
  • upper diameter: 15 cm
  • Spout diameter: 1.8 cm
  • Length of the funnel tube: 8 cm

The apparatus is shown in the drawing. According to the figure, the shaking channel is set up on a laboratory table. The rest of the apparatus should be arranged in such a way that the outlet of the shaking channel lies directly above the center of the funnel (3) and its distance from the top edge of the funnel is 5.5 cm

Ausführung :

  • 100 g der Probe werden über den Aufgabentrichter (1) in die Schüttelrinne (2) gebracht.
Execution :
  • 100 g of the sample are brought into the shaking channel (2) via the feed hopper (1).

Die Frequenz der Schüttelrinne soll 50 Hz betragen und der Öffnungsspalt so eingestellt sein, daß die Substanz die Schüttelrinne in 1 Minute durchlaufen hat.The frequency of the shaking trough should be 50 Hz and the opening gap should be set so that the substance has passed through the shaking trough in 1 minute.

Das Pulver fällt durch einen Trichter (3) und ein Einfüllrohr (4) in den darunter stehenden Innenzylinder der Testapparatur (5), während sich der Staub außerhalb dieses Gefäßes auf der Bodenplatte (6) des Außenzylinders (7) ansammelt.The powder falls through a funnel (3) and a filler pipe (4) into the inner cylinder of the test apparatus (5) below, while the dust outside this vessel accumulates on the base plate (6) of the outer cylinder (7).

Nach Beendigung des Pulverdurchlaufs durch die Schüttelrinne werden eventuell im Trichter verbliebene Pulverreste durch vorsichtiges Anklopfen des Trichters in die Apparatur überführt.After the powder has passed through the shaking trough, any remaining powder in the funnel is transferred into the apparatus by gently tapping the funnel.

Bei weniger staubigen Produkten läßt man 1 Minute absetzen, bei staubigem Material wird die Absetzzeit auf 2 Minuten ausgedehnt.If the product is less dusty, let it settle for 1 minute; if it is dusty, the settling time is extended to 2 minutes.

Der auf der blankpolierten Bodenplatte abgesetzte Staub wird mit einem Metallspatel in einem Wägeschälchen eingesammelt und zur Auswaage gebracht.The dust deposited on the polished floor plate is collected in a small bowl with a metal spatula and weighed out.

Der Staubgehalt wird in Prozent, bezogen auf die Einwaage, angegeben.The dust content is given in percent based on the weight.

Claims (1)

1. A granulated detergent builder consisting of 70 to 80% by weight of a water-insoluble silicate capable of binding calcium in the form of a finely divided, synthetic, water-insoluble crystalline compound containing bound water and corresponding to the following general formula
Figure imgb0015
in which
cat is a cation of valency n exchangeable with calcium, x is a number of 0.7 to 1.5, Me is boron or aluminium and y is a number of 0.8 to 6,
2 to 3% by weight nonionic surfactant
0 to 1% by weight alkali
0.5 to 5% by weight carboxymethyl cellulose and/or methyl cellulose

remainder water.
EP87117460A 1987-01-30 1987-11-26 Builder for washing agents Expired - Lifetime EP0279038B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP89123122A EP0368364B1 (en) 1987-01-30 1987-11-26 Builder for washing agents
AT87117460T ATE59675T1 (en) 1987-01-30 1987-11-26 DETERGENT BUILDER.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE3702763 1987-01-30
DE3702763 1987-01-30
DE19873735618 DE3735618A1 (en) 1987-01-30 1987-10-21 DETERGENT PICTURES
DE3735618 1987-10-21

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP89123122.7 Division-Into 1989-12-14

Publications (2)

Publication Number Publication Date
EP0279038A1 EP0279038A1 (en) 1988-08-24
EP0279038B1 true EP0279038B1 (en) 1991-01-02

Family

ID=25852033

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Application Number Title Priority Date Filing Date
EP89123122A Expired - Lifetime EP0368364B1 (en) 1987-01-30 1987-11-26 Builder for washing agents
EP87117460A Expired - Lifetime EP0279038B1 (en) 1987-01-30 1987-11-26 Builder for washing agents

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Application Number Title Priority Date Filing Date
EP89123122A Expired - Lifetime EP0368364B1 (en) 1987-01-30 1987-11-26 Builder for washing agents

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Country Link
US (1) US4883607A (en)
EP (2) EP0368364B1 (en)
JP (1) JPH0660319B2 (en)
AT (1) ATE106443T1 (en)
DE (3) DE3735618A1 (en)
DK (2) DK170031B1 (en)
ES (2) ES2053935T3 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3715051A1 (en) * 1987-05-06 1988-11-17 Degussa PHOSPHATE-FREE DETERGENT BUILDER
DE4109501A1 (en) * 1991-03-22 1992-09-24 Degussa AQUEOUS, STABLE SUSPENSION OF WATER-INSOLUBLE SILICATES CAPABLE OF CALCIUMIONS AND THE USE THEREOF FOR THE PRODUCTION OF DETERGENT AND CLEANING AGENTS
DE19525870A1 (en) * 1995-07-15 1997-01-16 Grueter Hans Jochen Preparing suspension of polysaccharide in liq. medium - includes dissolving or swelling stabiliser in non-aq. water sol. or water miscible medium, adding and stabilising polysaccharide
WO1997020020A1 (en) * 1995-11-29 1997-06-05 Unilever N.V. Detergent builder granule

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT335035B (en) * 1974-10-10 1977-02-25 Henkel & Cie Gmbh STABLE SUSPENSIONS OF WATER-INSOLUBLE, SILICATES CAPABLE OF BINDING CALCIUMIONS AND THEIR USE FOR THE MANUFACTURE OF DETERGENTS AND DETERGENTS
US4379080A (en) * 1981-04-22 1983-04-05 The Procter & Gamble Company Granular detergent compositions containing film-forming polymers
GB8415302D0 (en) * 1984-06-15 1984-07-18 Unilever Plc Fabric washing process
DE3504450A1 (en) * 1985-02-09 1986-08-14 Degussa Ag, 6000 Frankfurt DETERGENT PICTURES
DE3504451A1 (en) * 1985-02-09 1986-08-14 Degussa Ag, 6000 Frankfurt DETERGENT PICTURES

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ES2020253B3 (en) 1991-08-01
DE3735618A1 (en) 1988-08-11
US4883607A (en) 1989-11-28
ATE106443T1 (en) 1994-06-15
DK170716B1 (en) 1995-12-18
DK29588A (en) 1988-07-31
DE3766950D1 (en) 1991-02-07
DE3789971D1 (en) 1994-07-07
JPS63193996A (en) 1988-08-11
ES2053935T3 (en) 1994-08-01
EP0368364A2 (en) 1990-05-16
EP0279038A1 (en) 1988-08-24
DK170031B1 (en) 1995-05-01
EP0368364A3 (en) 1990-06-06
JPH0660319B2 (en) 1994-08-10
EP0368364B1 (en) 1994-06-01
DK19995A (en) 1995-02-24
DK29588D0 (en) 1988-01-22

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