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EP0279039B1 - Builder for washing agents - Google Patents

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Publication number
EP0279039B1
EP0279039B1 EP87117461A EP87117461A EP0279039B1 EP 0279039 B1 EP0279039 B1 EP 0279039B1 EP 87117461 A EP87117461 A EP 87117461A EP 87117461 A EP87117461 A EP 87117461A EP 0279039 B1 EP0279039 B1 EP 0279039B1
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Prior art keywords
water
weight
bis
calcium
zeolite
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EP87117461A
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German (de)
French (fr)
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EP0279039A1 (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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids

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 produced by spray drying an aqueous suspension of the zeolite powder with the addition of further detergent components.
  • An aluminum silicate can be used as a component according to the formula in the detergent builder according to the invention.
  • 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 I can be naturally occurring or else synthetically produced products, only the synthetically produced products being used in the present invention. They can be prepared, for example, by reacting 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 Si0 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.
  • 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 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 silicate particles can be different, for example in the range between 0.1 ⁇ m and 0.1 mm. This information relates to the primary particle size, ie the size of the particles obtained during the precipitation and, if appropriate, the subsequent crystallization. With 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 contain no primary or. Secondary particles more with diameters above 45 pm. Secondary particles are particles that are formed by agglomeration of the primary particles 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 be 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, 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 oil or tallow fatty alcohols, with oleyl alcohol or with secondary alcohols with 8-18, preferably 12-18 C atoms, and with mono- or dialkyl phenols with 6-14 C atoms are particularly important in the 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.
  • the water-soluble adducts of ethylene oxide with polypropylene glycol, alkylene diamine-polypropylene glycol and alkyl polypropylene glycols with 1-10 C atoms in the alkyl chain, in which the polypropylene glycol chain acts as a hydrophobic chain can be used as nonionic surfactants which contain 20-250 ethylene glycol ether groups and 10-100 propylene glycol ether groups.
  • Nonionic surfactants of the amine oxide or sulfoxide type can also be used.
  • nonionic surfactant is a mixture of at least two different fatty alcohol ethoxylates based on isotridecyl alcohol or an aliphatic C i g 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 be used.
  • R can be an aliphatic radical with 1 to 15, for example -CH 3 , -C2H "propyl, butyl, pentyl, hexyl, heptyl, octyl and nonyl, preferably with 9 carbon atoms such as nonyl.
  • the radical R can be in ortho, meta and / or para position.
  • Mixtures can also be used in which, in addition to p-substituted aryl ring, there is also o-substituted benzene ring. Mixtures are used in which 90% p-substitution and addition 10% there is an 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.
  • 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 will.
  • the proportion of carboxymethyl cellulose and / or methyl cellulose can be 1.0 to 2.5% by weight in a preferred embodiment of the invention.
  • 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 the amount of water and spray-drying the suspension thus obtained by known processes.
  • the granulated detergent builder according to the invention is stable in transportation, easy to redisperse and extremely low in 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 specified 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.
  • surfactants are used as a single component or in mixtures as a stabilizer:
  • 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.).
  • 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 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.
  • 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 tube (4) into the inner cylinder of the test apparatus (5) underneath, while the dust outside this vessel collects 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 base 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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

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 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 sprühzugrocknen und den übringen 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 mix them with 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.

Aus der EP-A 0 191 187 ist ein granulierter Waschmittelbuilder, der aus:

  • 65 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 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,
  • 4 bis 10 Gew.-% Natriumnitrilotriacetat
  • 1,5 bis 3 Gew.-% nichtionisches Tensid
  • 0 bis 1 Gew.-% Alkali
  • 0,5 bis 1,5 Gew.-% Carboxymethylcellulose und/oder Methylcellulose
  • Rest Wasser
EP-A 0 191 187 describes a granulated detergent builder which consists of:
  • 65 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,
  • 4 to 10% by weight sodium nitrilotriacetate
  • 1.5 to 3% by weight of nonionic surfactant
  • 0 to 1 wt% alkali
  • 0.5 to 1.5 wt .-% carboxymethyl cellulose and / or methyl cellulose
  • Rest of water

besteht, bekannt.exists, known.

Es ist weiterhin bekannt, granulierte Waschmittelbuilder, bestehend aus:

  • 70 bis 80 Gew.-% eines wasserunlöslichen, zum Binden von Calcium befähigen Silikates in Form einer feinverteilten, gebundenes Wasser enthaltenden, synthetisch hergestellten, wasserunlöslichen, kristallinen 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,
  • 4 bis 5 Gew.-% Natriumsulfat
  • 2 bis 3 Gew.-% nichtionisches Tensid
  • 0 bis 1 Gew.-% Alkali
  • 0,5 bis 1 Gew.-% Carboxymethylcellulose und/oder Methylcellulose
  • Rest Wasser
    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 silicate in the form of a finely divided, bound water-containing, synthetically produced, water-insoluble, crystalline 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,
  • 4 to 5% by weight sodium sulfate
  • 2 to 3% by weight of nonionic surfactant
  • 0 to 1 wt% alkali
  • 0.5 to 1 wt .-% carboxymethyl cellulose and / or methyl cellulose
  • Rest of water
    to be used for the production of phosphate-free detergents (DE-OS 35 04 450).

Diese bekannten Waschmittelbuilder haben den Nachteil, daß sie nur Zeolith A als alleinige aktive Komponente zur Wasserenthärtung enthalten. Bei der Konfektionierung phosphatfreier Waschmittel muß also immer eine Kobuilderkomponente - meist ein waserlöslicher Komplexbildner - zudosiert werden.These known detergent builders have the disadvantage that they contain only zeolite A as the sole active component for water softening. When packaging phosphate-free detergents, a kobuilder component - usually a water-soluble complexing agent - must always be added.

Gegenstand der Erfindung ist ein granulierter Waschmittelbuilder, bestehend aus:

  • 60 bis 80 Gew.-% eines wasserunlöslichen, zum Bilden von Calcium befähigten Silikates in Form einer feinverteilten, gebundenes Wasser enthaltenden, synthetisch hergestellten, wasserunlöslichen, kristallinen Verbindung der allgemeinen Formel
    Figure imgb0003
    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,
  • 0 bis 5 Gew.-% Natriumsulfat
  • 0 bis 3 Gew.-% nichtionisches Tensid
  • 0 bis 1 Gew.-% Carboxymethylcellulose und/oder Methylcellulose
  • 3 bis 10 Gew.-% Hydroxyethaniminodiacetat-di-Natriumsalz
  • Rest Wasser
The invention relates to a granulated detergent builder consisting of:
  • 60 to 80 wt .-% of a water-insoluble, capable of forming calcium silicate in the form of a finely divided, bound water-containing, synthetically produced, water-insoluble, crystalline compound of the general formula
    Figure imgb0003
     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,
  • 0 to 5% by weight sodium sulfate
  • 0 to 3% by weight of nonionic surfactant
  • 0 to 1 wt .-% carboxymethyl cellulose and / or methyl cellulose
  • 3 to 10% by weight of hydroxyethaniminodiacetate disodium salt
  • Rest of water

Die Verbindung Dinatriumsalz der Hydroxylethaniminodiessigsäure ist bekannt aus:

  • JP-OS 83/198598 (=CA 101 (2):914 h);
  • CA-PS 10 37 816 (=CA 90 (16):123493d);
  • US-PS 40 29 607 (=CA 87 (8):54914r).
The compound disodium salt of hydroxylethaniminodiacetic acid is known from:
  • JP-OS 83/198598 (= C A 101 (2): 914 h);
  • CA-PS 10 37 816 (= CA 90 (16): 123493d);
  • US-PS 40 29 607 (= CA 87 (8): 54914r).

In dem erfindungsgemäßen Waschmittelbuilder kann als Komponente gemäß der Formel ein Aluminiumsilikat eingesetzt werden.An aluminum silicate can be used as a component according to the formula in the detergent builder according to the invention.

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 I können natürlich vorkommende oder aber synthetisch hergestellte Produkte sein, wobei in der vorliegenden Erfindung nur die 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 Al(OH)2, A1203 oder Si02 lassen 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 I can be naturally occurring or else synthetically produced products, only the synthetically produced products being used in the present invention. They can be prepared, for example, by reacting 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 Si0 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 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 molecular formula comprises two types of different crystal structures (or their non-crystalline precursors), which also differ in their molecular formulas. They are:
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 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 getrocket 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 Aluminiumsilikatpartikel kann verschieden sein und z.B. im Bereich zwischen 0,1 um 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 um, insbesondere von 8 bis 0,1 um bestehen.The particle size of the individual aluminum silicate particles can be different, for example in the range between 0.1 μm and 0.1 mm. This information relates to the primary particle size, ie the size of the particles obtained during the precipitation and, if appropriate, the subsequent crystallization. With 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 pm. Als Sekundärteilchen werden Teilchen, die durch Agglomeration der Primärteilchen zu größeren Gebilden entstanden sind, bezeichnet.These aluminum silicates preferably contain no primary or. Secondary particles more with diameters above 45 pm. Secondary particles are particles that are formed by agglomeration of the primary particles 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 könen 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 oder DE-OS 26 51 485 hergestellt werden. Sie weisen dann die dort angegebenen Teilchenverteilungskurven auf.Such zeolite powder can be 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, 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 Dialkyl phenole 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 waserlöslichen 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 oil or tallow fatty alcohols, with oleyl alcohol or with secondary alcohols with 8-18, preferably 12-18 C atoms, and with mono- or dialkyl phenols with 6-14 C atoms are particularly important in the 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, Alkylendiamin-polypropylenglykol und Alkylpolypropylenglykole mit 1-10 C-Atomen in der Alkylkette brauchbar, in denen die Polypropylenglykolkette als hydrophober Rest fungiert.Furthermore, the water-soluble adducts of ethylene oxide with polypropylene glycol, alkylene diamine-polypropylene glycol and alkyl polypropylene glycols with 1-10 C atoms in the alkyl chain, in which the polypropylene glycol chain acts as a hydrophobic chain, can be used as nonionic surfactants which contain 20-250 ethylene glycol ether groups and 10-100 propylene glycol ether groups.

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 Cig-Alkohol und Ethylenoxid. Dieses Gemisch kann bevorzugterweise aus Fettalkoholethoxylaten mit 4,5 bis 5,5 EO und Fettalkoholethoxylaten mit 6 bis 8 EO bestehen.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 i g 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.

Weiterhin kann als nichhtionisches Tensid eine Mischung von mindestens zwei verschiedenen Alkylphenoläthoxylaten der Formel

Figure imgb0007
verwendet werden.A mixture of at least two different alkylphenol ethoxylates of the formula can also be used as the nonionic surfactant
Figure imgb0007
 be used.

R kann dabei ein aliphatischer Rest mit 1 bis 15, beispielsweise -CH3, -C2H" 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 para-Stellung substituiert sein. Es können auch Gemische eingesetzt werden, in denen neben p-substituiertem Arylring auch o-substituierter Benzolring vorhanden ist. Es werden Gemische eingesetzt, in denen zu 90% eine p-Substitution und zu 10% eine ortho-Substitution vorliegt.R can be an aliphatic radical with 1 to 15, for example -CH 3 , -C2H "propyl, butyl, pentyl, hexyl, heptyl, octyl and nonyl, preferably with 9 carbon atoms such as nonyl. The radical R can be in ortho, meta and / or para position. Mixtures can also be used in which, in addition to p-substituted aryl ring, there is also o-substituted benzene ring. Mixtures are used in which 90% p-substitution and addition 10% there is an 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.

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 der R = 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 will. 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 1,0 bis 2,5 Gew.-% betragen.The proportion of carboxymethyl cellulose and / or methyl cellulose can be 1.0 to 2.5% by weight in a preferred embodiment of the invention.

Die Herstellung des erfindungsgemäßen granulatförmigen Waschmittelbuilders kann erfolgen, indem man die einzelnen Komponenten miteinander vermischt, eine für eine Sprühtrocknung geeignete Konsistenz durch der Wasermenge einstellot und die so erhaltene Suspension nach bekannten Verfahren sprühtrocknet.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 the amount of water and spray-drying the suspension thus obtained by known processes.

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 in 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.

Dieses Ergebis war aufgrund der schlechten Fließeigenschaften des Zeolithpulvers sowie des Dinatriumsalzes der Hydroxyethaniminodiessigsäure nicht zu erwarten.This result was not to be expected due to the poor flow properties of the zeolite powder and the disodium salt of hydroxyethaniminodiacetic acid.

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 Teilchensprektrum 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 specified 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 werden die folgenden Tenside als einzige Komponente oder in Mischungen als Stabilisator eingesetzt:

Figure imgb0008
The following surfactants are used as a single component or in mixtures as a stabilizer:
Figure imgb0008

Die erhaltene Suspension wird mit den übrigen in den Tabellen aufgeführten Bestandteilen vermischt und anschließend sprühgetrocknet (Düsentrockner Eingangstemperatur 180°C, Ablufttemperatur 75°C).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 Ergebnisse sind in der folgenden Tabelle I aufgeführt:

Figure imgb0009
The results are shown in Table I below:
Figure imgb0009

Der Staubtest nach Dr. Groschopp wird wie folgt durchgeführt:The dust test according to Dr. Groschopp is carried out as follows:

Das über eine Schüttelrinne in einen Zylinder fallende 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:

  • Apparatur zur Bestimmung des Staubes, bestehend aus Schüttelrinne
  • Hersteller: AEG, Typ DR 50
  • 220 V 50 Hz, 0,15 A.
The powder falling into a cylinder via a shaking trough 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:
  • 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
Outer cylinder
  • Height: 70 cm, diameter 40 cm
  • closed at the top, open at the bottom

Die Deckplatte ist in der Mitte mit einer kreisförmigen Öffnung (Durchmesser: 3 cm) zur Aufnahme des Einfüllrohres versehen.

  • Innenzylinder
  • Höhe: 10 cm, Durchmesser: 18 cm
  • unten geschlossen, oben offen. Bodenplatte
  • Form: Rund
  • Durchmesser: 48 cm Einfüllrohr
  • Länge: 30 cm, Durchmesser: 2,5 cm
  • Eintauchtiefe des Rohres in den Außenzylinder: 20 cm.
The cover plate is provided in the middle with a circular opening (diameter: 3 cm) for receiving the filler pipe.
  • Inner cylinder
  • Height: 10 cm, diameter: 18 cm
  • closed at the bottom, open at the top. Base plate
  • Shape: round
  • Diameter: 48 cm filler tube
  • 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
funnel
  • upper diameter: 15 cm
  • Spout diameter: 1.8 cm
  • Length of the funnel tube: 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 beträgt.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 Aufgabetrichter (1) in die Schüttelrinne (2) gebracht.
Execution:
  • 100 g of the sample are brought into the shaking channel (2) via the feed funnel (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 tube (4) into the inner cylinder of the test apparatus (5) underneath, while the dust outside this vessel collects 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 blank polierten Bodenplatte abgesetzte Staub wird mit einem Metallspatel in einem Wägeschälchen eingesammelt und zur Auswaage gebracht.The dust deposited on the polished base plate is collected in a small bowl with a metal spatula and weighed out.

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

Claims (2)

1. A granulated detergent builder consisting of 60 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 imgb0012
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,
0 to 5% by weight sodium sulfate
0 to 3% by weight nonionic surfactant
0 to 2,5% by weight carboxymethyl cellulose and/or methyl cellulose
3 to 10% by weight hydroxyethaneimino diacetate, disodium salt
remainder water.
2. The use of the granulated detergent builder claimed in claim 1 for the production of phosphate-free detergents.
EP87117461A 1987-01-30 1987-11-26 Builder for washing agents Expired - Lifetime EP0279039B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87117461T ATE59854T1 (en) 1987-01-30 1987-11-26 DETERGENT BUILDER.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE3702761 1987-01-30
DE3702761 1987-01-30
DE19873735617 DE3735617A1 (en) 1987-01-30 1987-10-21 DETERGENT PICTURES
DE3735617 1987-10-21

Publications (2)

Publication Number Publication Date
EP0279039A1 EP0279039A1 (en) 1988-08-24
EP0279039B1 true EP0279039B1 (en) 1991-01-09

Family

ID=25852032

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87117461A Expired - Lifetime EP0279039B1 (en) 1987-01-30 1987-11-26 Builder for washing agents

Country Status (4)

Country Link
EP (1) EP0279039B1 (en)
DE (2) DE3735617A1 (en)
DK (1) DK29688A (en)
ES (1) ES2020254B3 (en)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4029607A (en) * 1974-03-29 1977-06-14 The Drackett Company Drain cleaning compositions
DE3504450A1 (en) * 1985-02-09 1986-08-14 Degussa Ag, 6000 Frankfurt DETERGENT PICTURES

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ES2020254B3 (en) 1991-08-01
DE3767299D1 (en) 1991-02-14
EP0279039A1 (en) 1988-08-24
DK29688A (en) 1988-07-31
DE3735617A1 (en) 1988-08-11
DK29688D0 (en) 1988-01-22

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