EP0432437A1 - Granular, alkaline and phosphate-free detergent additive - Google Patents

Granular, alkaline and phosphate-free detergent additive Download PDF

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Publication number
EP0432437A1
EP0432437A1 EP90121008A EP90121008A EP0432437A1 EP 0432437 A1 EP0432437 A1 EP 0432437A1 EP 90121008 A EP90121008 A EP 90121008A EP 90121008 A EP90121008 A EP 90121008A EP 0432437 A1 EP0432437 A1 EP 0432437A1
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Prior art keywords
weight
component
composition according
parts
grains
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EP90121008A
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German (de)
French (fr)
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EP0432437B1 (en
Inventor
Lothar Pioch
Wolfgang Dr. Seiter
Ulrich Dr. Jahnke
Ernst-Walter Dr. Hoffman
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
    • C11D11/02—Preparation in the form of powder by spray drying
    • 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
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • the present invention relates to a granular, phosphate-free cleaning additive which is suitable for cleaning hard surfaces, for example as an additional component in dishwashing detergents. Due to its good lime binding properties, it can be used as an additive to wash water in hard water areas and can replace the polymer phosphates commonly used for this purpose. Agents of this type are also suitable for the pretreatment of hard water intended for hashing, rinsing and cleaning purposes. They are usually stored separately from granular hash and cleaning agents and, if necessary, used together with them in hash or cleaning processes. In the sense of an additional builder effect, they improve the cleaning ability of the actual hash and cleaning agent and prevent the formation of hard limescale deposits on the heating elements or on the textile fiber. In special cases, the detergents can be added to granular detergents or further processed together with them, whereby they advantageously influence their pouring properties and flushing behavior or enable trouble-free further processing.
  • salts of polymeric aliphatic carboxylic acids include in particular salts of poly acrylic acid and polymethacrylic acid and copolymers of these two acids with maleic acid and / or vinyl esters. It is not difficult to produce storage-stable granules which contain up to about 15% by weight of such polymer salts. This applies in particular if the granules contain water-insoluble, finely divided zeolites or clays. To the best of our knowledge, granules with higher proportions of such salts cannot readily be converted into stable granules, especially if they do not contain any water-binding or water-repellent mixture constituents or are mixed exclusively with water-soluble neutral salts or builder salts.
  • DE 21 00 500-82 (US Pat. No. 3,933,673) proposes using the polymers as free acids or partially neutralized salts with a degree of neutralization of at most 60% or converting them from their aqueous solutions into granular products by hot spray drying.
  • the polymeric carboxylic acids develop their full activity only as completely neutralized salts.
  • the alkali required for neutralization must therefore be subsequently added to the acidic granules, which requires an additional process step and carries the risk that the mixtures partially separate during transport.
  • Component (a) consists of homopolymeric or copolymeric carboxylic acids in the form of the sodium salts.
  • Suitable homopolymers are polymethacrylic acid and preferably polyacrylic acid, for example those with a molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymers are those of acrylic acid with methacrylic acid and preferably of the copolymers of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid as are characterized, for example, in EP 25551-81, have proven to be particularly suitable. These are copolymers containing 50 to 90% by weight. Contain acrylic acid and 50 to 10 wt .-% maleic acid. Copolymers in which 60 to 85% by weight of acrylic acid and 40 to 15% by weight of maleic acid are present are particularly preferred.
  • Your molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000.
  • Mixtures of different homo- and copolymers can also be used with advantage, in particular mixtures of homopolymeric acrylic acid and the copolymers of 50 to 90% by weight of acrylic acid and 50 to 10 96 maleic acid described above.
  • Such mixtures which are characterized by favorable grain properties and high storage stability, can consist, for example, of 10 to 50% by weight of homopolymeric acrylic acid and 90 to 50% by weight of acrylic acid-maleic acid copolymers.
  • Highly polymeric polyacrylic acids can also be used in these mixtures which, when used alone, have a slightly greater tendency to stick or melt than the low molecular weight polyacrylates.
  • the sodium carbonate (b) and the sodium sulfate (c) are used in anhydrous form. With proportions of sodium carbonate of approx. 40% by weight and more, it is advisable to reduce the hate content (d) of the compositions to less than 6% by weight or to choose a somewhat higher proportion of sodium sulfate, for example in the range 8 to 15% by weight. Sodium sulfate contents of more than 10% by weight, for example 15 to 20% by weight, fundamentally improve the grain properties and the shelf life of the compositions. On the other hand, sodium sulfate is ineffective fiber when using the agents, which is why its proportion should be as low as possible.
  • fractions of 5 to 6% by weight (c) are sufficient to contain agents with a content of approx. 50% by weight (a), approx. 40% by weight (b) and approx To stabilize 4% by weight (d) and to ensure good flow properties.
  • the agents can also contain minor components such as dyes and color pigments and can be colored uniformly or speckled.
  • the proportion of such minor components is well below 1% by weight.
  • the average grain size of the agent is usually 0.2 to 1.2 mm, the proportion of the grains being below 0.1 mm not more than 2% by weight and above 2 mm not more than 20% by weight.
  • at least 80% by weight, in particular at least 90% by weight, of the grains have a size of 0.2 to 1.6 mm, the proportion of the grains between 0.1 and 0.05 mm not more than 3% by weight %, in particular not more than 1% by weight and the proportion of the grains between 1.6 and 2.4 mm is not more than 20% by weight, in particular not more than 10% by weight. Larger proportions of fine grain generally lead to a deterioration in the induction behavior.
  • the bulk density is 350 to 550 g / l.
  • the granules are produced by spray drying an aqueous slurry.
  • the slurry concentration is between 50 and 68% by weight (non-aqueous fraction), preferably between 55 and 60% by weight, the decisive factor being the viscosity of the paste, which should not exceed 10,000 mpa.s and advantageously 2,500 to 6,000 mpa ⁇ s.
  • the temperature of the slurry is usually between 50 and 100 ° C.
  • the pressure at the spray nozzles is generally 30 to 80 bar, preferably 40 to 70 bar.
  • the temperature of the counter-current dry gases. in the entrance zone of the spray tower, ie in the so-called ring channel is advantageously between 200 and 320 ° C, in particular between 220 and 300 ° C.
  • the drying is preferably carried out in such a way that the hater bond is reduced to less than 1 mol of H2O per mol of sodium carbonate, in particular to 0.3 to 0.7 mol of H2O per mol of sodium carbonate.
  • Conventional spray drying systems can be used for spray drying, it being possible for the spray nozzles to be arranged in one or more levels.
  • the spray material leaving the tower can, if necessary after cooling with flowing air, be immediately further processed or packaged.
  • the granules are exceptionally free-flowing and can be washed into residue-free washing machines and dishwashers and retain these advantageous properties even after a long storage period.
  • a granular composition (in% by weight) 50.0% acrylic acid-maleic acid copolymer (MW 70,000) in the form of the Na salt 36.3% sodium carbonate 10.0% sodium sulfate 3.7% haters was made as follows:
  • a slurry which contained the abovementioned solids and 44.5% by weight of water and had a viscosity of 4,500 mpa ⁇ s at a processing temperature of 63 ° C. was sprayed into a drying tower at a pressure of 40 bar via nozzles.
  • the counter-current dry gas had a temperature of 240 ° C in the ring channel and 120 ° C in the area of the tower outlet.
  • the spray product was extremely free-flowing and had a bulk density of 450 g / l.
  • the dust content ( ⁇ 0.05 mm) was less than 0.02% by weight.
  • the water binding was 0.6 moles of water per mole of sodium carbonate.
  • Example 2 As described in Example 1, a free-flowing, storage-stable granulate of the following composition was produced by spray drying: 50.0% by weight Na salt of the acrylic acid-maleic acid copolymer, 40.8% by weight sodium carbonate, 5.0% by weight sodium sulfate, 4.2% by weight haters.
  • the dust content was less than 0.02% by weight.
  • the spray product showed an equally good flowability as the product according to Example 1, but it decreased slightly over a period of several weeks.
  • the product is therefore particularly suitable as an admixture component for granular detergents or for further processing into granular dishwashing detergents, this small tendency toward reduced free-flowing ability, which only develops after long storage, no longer occurs.
  • experiment A the same spray conditions were used as described in example 1, in experiment B the tower outlet temperature of the dry gases was 90 ° C. Both spray products consisted of sticky grains that could already be deformed under slight pressure. The flow behavior was unsatisfactory and when trying to process the products together with other detergent components into stable granules, problems occurred due to sticking to the mixing elements and the inner wall of the granulating mixer.

Abstract

The additive can be obtained by spray drying and contains (a) 35 to 60 % by weight of sodium salts of at least one homopolymeric or copolymeric (meth)acrylic acid, (b) 25 to 50 % by weight of sodium carbonate (calculated anhydrous), (c) 4 to 20 % by weight of sodium sulphate (calculated anhydrous) and (d) 1 to 7 % by weight of water and is distinguished by favourable particle properties and good storage stability.

Description

Gegenstand der vorliegenden Erfindung ist ein granulares, phos­phatfreies Reinigungsadditiv, das sich zum Reinigen harter Ober­flächen, beispielsweise als Zusatzkomponente in Geschirrspülmit­teln eignet. Aufgrund seiner guten Kalkbindungseigenschaften kann es als Zusatz zur Waschlauge in Hartwassergebieten verwendet wer­den und vermag die hierfür üblicherweise verwendeten Polymerphos­phate zu ersetzen. Mittel dieser Art eignen sich außerdem zur Vor­behandlung von hartem, für Hasch-, Spül- und Reinigungszwecke be­stimmtem Wasser. Sie werden üblicherweise separat von granularen Hasch- und Reinigungsmitteln aufbewahrt und, je nach Bedarf, zu­sammen mit diesen in Hasch- oder Reinigungsprozessen eingesetzt. Sie verbessern im Sinne einer zusätzlichen Builderwirkung das Rei­nigungsvermögen des eigentlichen Hasch- und Reinigungsmittels und verhindern die Ausbildung harter Kalkniederschläge auf den Heiz­elementen bzw. auf der Textilfaser. Die Mittel können in besonde­ren Fällen granularen Reinigungsmitteln zugemischt oder mit diesen zusammen weiterverarbeitet werden, wobei sie deren Rieseleigen­schaften und Einspülverhalten vorteilhaft beeinflussen bzw. eine störungsfreie Weiterverarbeitung ermöglichen.The present invention relates to a granular, phosphate-free cleaning additive which is suitable for cleaning hard surfaces, for example as an additional component in dishwashing detergents. Due to its good lime binding properties, it can be used as an additive to wash water in hard water areas and can replace the polymer phosphates commonly used for this purpose. Agents of this type are also suitable for the pretreatment of hard water intended for hashing, rinsing and cleaning purposes. They are usually stored separately from granular hash and cleaning agents and, if necessary, used together with them in hash or cleaning processes. In the sense of an additional builder effect, they improve the cleaning ability of the actual hash and cleaning agent and prevent the formation of hard limescale deposits on the heating elements or on the textile fiber. In special cases, the detergents can be added to granular detergents or further processed together with them, whereby they advantageously influence their pouring properties and flushing behavior or enable trouble-free further processing.

Bestandteil vieler derartiger Mittel sind Salze polymerer alipha­tischer Carbonsäuren. Hierzu zählen insbesondere Salze der Poly­ acrylsäure und Polymethacrylsäure sowie von Copolymeren dieser beiden Säuren mit Maleinsäure und/oder Vinylestern. Es bereitet keine Schwierigkeiten, lagerbeständige Granulate herzustellen, die bis zu ca. 15 Gew.-% derartiger Polymersalze enthalten. Dies gilt insbesondere dann, wenn die Granulate wasserunlösliche, feintei­lige Zeolithe bzw. Tone enthalten. Granulate mit höheren Anteilen an solchen Salzen lassen sich nach bisheriger Kenntnis nicht ohne weiteres in stabile Granulate überführen, insbesondere dann nicht, wenn sie keine wasserbindenden oder wasserabweisenden Mischungsbe­standteile enthalten oder ausschließlich mit wasserlöslichen Neu­tralsalzen oder Buildersalzen vermischt sind.Many such agents include salts of polymeric aliphatic carboxylic acids. These include in particular salts of poly acrylic acid and polymethacrylic acid and copolymers of these two acids with maleic acid and / or vinyl esters. It is not difficult to produce storage-stable granules which contain up to about 15% by weight of such polymer salts. This applies in particular if the granules contain water-insoluble, finely divided zeolites or clays. To the best of our knowledge, granules with higher proportions of such salts cannot readily be converted into stable granules, especially if they do not contain any water-binding or water-repellent mixture constituents or are mixed exclusively with water-soluble neutral salts or builder salts.

In DE 21 00 500-82 (US 3 933 673) wird zur Lösung dieses Problems vorgeschlagen, die Polymeren als freie Säuren oder teilneutrali­sierte Salze mit einem Neutralisationsgrad von maximal 60 % ein­zusetzen bzw. aus ihren wäßrigen Lösungen durch Heißsprühtrocknen in körnige Produkte zu überführen. Wie jedoch in diesem Dokument betont wird, entfalten die polymeren Carbonsäuren ihre volle Hir­kung nur als vollständig neutralisierte Salze. Das zur Neutrali­sation benötigte Alkali muß daher den sauren Granulaten nachträg­lich zugemischt werden, was einen zusätzlichen Verfahrensschritt erfordert und die Gefahr birgt, daß sich die Gemische beim Trans­port teilweise entmischen.To solve this problem, DE 21 00 500-82 (US Pat. No. 3,933,673) proposes using the polymers as free acids or partially neutralized salts with a degree of neutralization of at most 60% or converting them from their aqueous solutions into granular products by hot spray drying. However, as is emphasized in this document, the polymeric carboxylic acids develop their full activity only as completely neutralized salts. The alkali required for neutralization must therefore be subsequently added to the acidic granules, which requires an additional process step and carries the risk that the mixtures partially separate during transport.

Es wurde nun überraschend gefunden, daß definierte Salzgemische mit einem vergleichsweise hohen Gehalt &n Salzen polymerer Carbonsäuren hergestellt werden können, die als Granulate lagerbe­ständig und gut rieselfähig sind und somit nicht dje Nachteile der bekannten Mittel besitzen.It has now surprisingly been found that defined salt mixtures can be produced with a comparatively high content of polymeric carboxylic acids which are storage-stable and free-flowing as granules and thus do not have the disadvantages of the known agents.

Gegenstand der Erfindung ist ein granulares, alkalisches, phos­phatfreies Reinigungsadditiv, enthaltend im wesentlichen

  • (a) 35 bis 60 Gew. -% an Natriumsalzen mindestens einer homopoly­meren bzw. copolymeren (Meth-)Acrylsäure,
  • (b) 25 bis 50 Gew.-% Natriumcarbonat (wasserfrei gerechnet),
  • (c) 4 bis 20 Gew.-% Natriumsulfat (wasserfrei gerechnet),
  • (d) 1 bis 7 Gew. -% Hasser.
The invention relates to a granular, alkaline, phosphate-free cleaning additive, comprising essentially
  • (a) 35 to 60% by weight of sodium salts of at least one homopolymeric or copolymeric (meth) acrylic acid,
  • (b) 25 to 50% by weight of sodium carbonate (calculated as anhydrous),
  • (c) 4 to 20% by weight of sodium sulfate (calculated as anhydrous),
  • (d) 1 to 7% by weight haters.

Im Rahmen bevorzugter Ausführungsformen betragen die Anteile der Komponenten:

  • (a) 40 bis 55 Gew. -96, insbesondere 45 bis 52 Gew. -%,
  • (b) 30 bis 45 Gew. -%, insbesondere 30 bis 38 Gew. -%,
  • (c) 5 bis 15 Gew. -%, insbesondere 5 bis 10 Gew. -%,
  • (d) 2 bis 6 Gew. -%, insbesondere 3 bis 5 Gew. -%.
In the context of preferred embodiments, the proportions of the components are:
  • (a) 40 to 55% by weight, in particular 45 to 52% by weight,
  • (b) 30 to 45% by weight, in particular 30 to 38% by weight,
  • (c) 5 to 15% by weight, in particular 5 to 10% by weight,
  • (d) 2 to 6% by weight, in particular 3 to 5% by weight.

Die Komponente (a) besteht aus homopolymeren bzw. copolymeren Carbonsäuren in Form der Natriumsalze. Geeignete Homopolymere sind Polymethacrylsäure und bevorzugt Polyacrylsäure, beispielsweise solche mit einem Molekulargewicht von 800 bis 150 000 (auf Säure bezogen). Herden ausschließlich homopolymere Polyacrylsäuren (in Salzform) verwendet, beträgt deren Molekulargewicht im Interesse einer guten Rieselfähigkeit und Lagerbeständigkeit vorzugsweise 1 000 bis 80 000 (auf Säure bezogen).Component (a) consists of homopolymeric or copolymeric carboxylic acids in the form of the sodium salts. Suitable homopolymers are polymethacrylic acid and preferably polyacrylic acid, for example those with a molecular weight of 800 to 150,000 (based on acid). Herds used exclusively homopolymeric polyacrylic acids (in salt form), their molecular weight is preferably 1,000 to 80,000 (based on acid) in the interest of good flowability and storage stability.

Geeignete Copolymere sind solche der Acrylsäure mit Methacrylsäure und vorzugsweise der Copolymere der Acrylsäure oder Methacrylsäure mit Maleinsäure. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Maleinsäure erwiesen, wie sie beispielsweise in EP 25551-81 charakterisiert sind. Es handelt sich dabei um Copolyme­risate, die 50 bis 90 Gew.-%. Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Besonders bevorzugt sind solche Copolymere, in den 60 bis 85 Gew. -% Acrylsäure und 40 bis 15 Gew. -% Malein­säure vorliegen. Ihr Molekulargewicht, bezogen auf freie Säuren, beträgt im allgemeinen 5 000 bis 200 000, vorzugsweise 10 000 bis 120 000.Suitable copolymers are those of acrylic acid with methacrylic acid and preferably of the copolymers of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid, as are characterized, for example, in EP 25551-81, have proven to be particularly suitable. These are copolymers containing 50 to 90% by weight. Contain acrylic acid and 50 to 10 wt .-% maleic acid. Copolymers in which 60 to 85% by weight of acrylic acid and 40 to 15% by weight of maleic acid are present are particularly preferred. Your molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000.

Mit Vorteil lassen sich auch Gemische verschiedener Homo- und Co­polymerer einsetzen, insbesondere Gemische aus homopolymerer Acrylsäure und den vorstehend beschriebenen Copolymeren aus 50 bis 90 Gew. -% Acrylsäure und 50 bis 10 96 Maleinsäure. Derartige Gemi­sche, die sich durch günstige Korneigenschaften und hohe Lagerbe­ständigkeit auszeichnen, können zum Beispiel aus 10 bis 50 Gew.-% homopolymerer Acrylsäure und 90 bis 50 Gew.-% Acrylsäure-Malein­säure-Copolymeren bestehen. In diesen Gemischen können auch hoch­polymere Polyacrylsäuren mitverwendet werden, die bei alleinigem Einsatz etwas mehr zum Kleben bzw. Zerfließen der Körner neigen als niedermolekulare Polyacrylate.Mixtures of different homo- and copolymers can also be used with advantage, in particular mixtures of homopolymeric acrylic acid and the copolymers of 50 to 90% by weight of acrylic acid and 50 to 10 96 maleic acid described above. Such mixtures, which are characterized by favorable grain properties and high storage stability, can consist, for example, of 10 to 50% by weight of homopolymeric acrylic acid and 90 to 50% by weight of acrylic acid-maleic acid copolymers. Highly polymeric polyacrylic acids can also be used in these mixtures which, when used alone, have a slightly greater tendency to stick or melt than the low molecular weight polyacrylates.

Das Natriumcarbonat (b) und das Natriumsulfat (c) werden in was­serfreier Form eingesetzt. Bei Anteilen an Natriumcarbonat von ca. 40 Gew.-% und mehr empfiehlt es sich, den Hassergehalt (d) der Mittel auf weniger als 6 Gew.-% zu senken oder den Anteil an Na­triumsulfat etwas höher zu wählen, beispielsweise im Bereich 8 bis 15 Gew.-%. Anteile an Natriumsulfat von über 10 Gew.-%, bei­spielsweise 15 bis 20 Gew.-% verbessern grundsätzlich die Kornei­genschaften und die Lagerbeständigkeit der Mittel. Andererseits ist Natriumsulfat bei der Anwendung der Mittel unwirksamer Bal­laststoff, weshalb sein Anteil möglichst gering sein sollte. Es ist sehr überraschend, daß bereits Anteile von 5 bis 6 Gew.-% (c) ausreichen, um Mittel mit einem Gehalt von ca. 50 Gew.-% (a), ca. 40 Gew.-% (b) und ca. 4 Gew.-% (d) zu stabilisieren und gute Rieseleigenschaften zu gewährleisten.The sodium carbonate (b) and the sodium sulfate (c) are used in anhydrous form. With proportions of sodium carbonate of approx. 40% by weight and more, it is advisable to reduce the hate content (d) of the compositions to less than 6% by weight or to choose a somewhat higher proportion of sodium sulfate, for example in the range 8 to 15% by weight. Sodium sulfate contents of more than 10% by weight, for example 15 to 20% by weight, fundamentally improve the grain properties and the shelf life of the compositions. On the other hand, sodium sulfate is ineffective fiber when using the agents, which is why its proportion should be as low as possible. It is very surprising that fractions of 5 to 6% by weight (c) are sufficient to contain agents with a content of approx. 50% by weight (a), approx. 40% by weight (b) and approx To stabilize 4% by weight (d) and to ensure good flow properties.

Weiterhin können die Mittel noch Minderbestandteile, wie Farb­stoffe und Farbpigmente, enthalten und einheitlich oder gespren­kelt angefärbt sein. Der Anteil derartiger Minderbestandteile liegt deutlich unter 1 Gew.-%.The agents can also contain minor components such as dyes and color pigments and can be colored uniformly or speckled. The proportion of such minor components is well below 1% by weight.

Die mittlere Korngröße des Mittels beträgt üblicherweise 0,2 bis 1,2 mm, wobei der Anteil der Körner unterhalb 0,1 mm nicht mehr als 2 Gew.-% und oberhalb 2 mm nicht mehr als 20 Gew.-% beträgt. Vorzugsweise weisen mindestens 80 Gew.-%, insbesondere mindestens 90 Gew.-% der Körner eine Größe von 0,2 bis 1,6 mm auf, wobei der Anteil der Körner zwischen 0,1 und 0,05 mm nicht mehr als 3 Gew.-%, insbesondere nicht mehr als 1 Gew.-% und der Anteil der Körner zwischen 1,6 und 2,4 mm nicht mehr als 20 Gew.-%, insbe­sondere nicht mehr als 10 Gew.-% beträgt. Größere Anteile an Feinkorn führen in der Regel zu einer Verschlechterung des Ein­spülverhaltens. Das Schüttgewicht beträgt 350 bis 550 g/l.The average grain size of the agent is usually 0.2 to 1.2 mm, the proportion of the grains being below 0.1 mm not more than 2% by weight and above 2 mm not more than 20% by weight. Preferably, at least 80% by weight, in particular at least 90% by weight, of the grains have a size of 0.2 to 1.6 mm, the proportion of the grains between 0.1 and 0.05 mm not more than 3% by weight %, in particular not more than 1% by weight and the proportion of the grains between 1.6 and 2.4 mm is not more than 20% by weight, in particular not more than 10% by weight. Larger proportions of fine grain generally lead to a deterioration in the induction behavior. The bulk density is 350 to 550 g / l.

Die Herstellung der Granulate erfolgt durch Sprühtrocknung eines wäßrigen Slurries. Die Slurrykonzentration liegt zwischen 50 und 68 Gew.-% (nichtwäßriger Anteil), vorzugsweise zwischen 55 und 60 Gew. -96, wobei die Viskosität der Paste maßgebend ist, die 10 000 mpa·s nicht überschreiten sollte und vorteilhaft 2 500 bis 6 000 mpa·s beträgt. Die Temperatur des Slurries liegt üblicherweise zwischen 50 und 100 °C. Der Druck an den Sprühdüsen beträgt im allgemeinen 30 bis 80 bar, vorzugsweise 40 bis 70 bar. Die Tempe­ratur der im Gegenstrom geführten Trockengase. in der Eingangszone des Sprühturms, d.h. im sogenannten Ringkanal, liegt vorteilhaft zwischen 200 und 320 °C, insbesondere zwischen 220 und 300 °C. Im Bereich des Turmaustritts soll sie zwischen 100 und 130 °C, vor­zugsweise zwischen 110 und 125 °C liegen. Derart vergleichsweise hohe Betriebstemperaturen sind für die Herstellung eines einwand­freien Produktes von Vorteil und trotz des hohen Anteils an brenn­barer organischer Substanz im Sprühprodukt nicht kritisch, da die Selbstenzündungstemperatur oberhalb 330 °C liegt. Im Interesse günstiger Korneigenschaften wird die Trocknung vorzugsweise so geleitet, daß die Hasserbindung auf weniger als 1 Mol H₂O pro Mol Natriumcarbonat, insbesondere auf 0,3 bis 0,7 Mol H₂O pro Mol Na­triumcarbonat gesenkt wird. Zur Sprühtrocknung können übliche Sprühtrocknungsanlagen (Sprühtürme) eingesetzt werden, wobei die Sprühdüsen in einer oder mehreren Ebenen angeordnet sein können.The granules are produced by spray drying an aqueous slurry. The slurry concentration is between 50 and 68% by weight (non-aqueous fraction), preferably between 55 and 60% by weight, the decisive factor being the viscosity of the paste, which should not exceed 10,000 mpa.s and advantageously 2,500 to 6,000 mpa · s. The temperature of the slurry is usually between 50 and 100 ° C. The pressure at the spray nozzles is generally 30 to 80 bar, preferably 40 to 70 bar. The temperature of the counter-current dry gases. in the entrance zone of the spray tower, ie in the so-called ring channel, is advantageously between 200 and 320 ° C, in particular between 220 and 300 ° C. In the area of the tower outlet it should be between 100 and 130 ° C, preferably between 110 and 125 ° C. Such comparatively high operating temperatures are advantageous for the production of a perfect product and, despite the high proportion of flammable organic substance in the spray product, are not critical, since the Auto-ignition temperature is above 330 ° C. In the interest of favorable grain properties, the drying is preferably carried out in such a way that the hater bond is reduced to less than 1 mol of H₂O per mol of sodium carbonate, in particular to 0.3 to 0.7 mol of H₂O per mol of sodium carbonate. Conventional spray drying systems (spray towers) can be used for spray drying, it being possible for the spray nozzles to be arranged in one or more levels.

Das den Turm verlassende Sprühgut kann, gegebenenfalls nach Küh­lung mit strömender Luft, unmittelbar weiterverarbeitet bzw. ab­gepackt werden. Die Granulate sind hervorragend rieselfähig und rückstandslos in Hasch- und Spülmaschinen einspülbar und behalten diese vorteilhaften Eigenschaften auch nach längerer Lagerzeit.The spray material leaving the tower can, if necessary after cooling with flowing air, be immediately further processed or packaged. The granules are exceptionally free-flowing and can be washed into residue-free washing machines and dishwashers and retain these advantageous properties even after a long storage period.

BeispieleExamples

1. Ein granulares Mittel der Zusammensetzung (in Gew.-%)
50,0 % Acrylsäure-Maleinsäure-Copolymer (MG = 70 000) in Form des Na-Salzes
36,3 % Natriumcarbonat
10,0 % Natriumsulfat
3,7 % Hasser
wurde wie folgt hergestellt:1. A granular composition (in% by weight)
50.0% acrylic acid-maleic acid copolymer (MW = 70,000) in the form of the Na salt
36.3% sodium carbonate
10.0% sodium sulfate
3.7% haters
was made as follows:

Ein Slurry, der die vorgenannten Feststoffe und 44,5 Gew.-% Wasser enthielt und eine Viskosität von 4 500 mpa·s bei der Verarbeitungstemperatur von 63 °C aufwies, wurde mit einem Druck von 40 bar über Düsen in einen Trockenturm versprüht. Das im Gegenstrom geführte Trockengas wies eine Temperatur von 240 °C im Ringkanal und 120 °C im Bereich des Turmaustritts auf. Das Sprühprodukt war hervorragend rieselfähig und wies ein Schüttgewicht von 450 g/l auf. Durch Siebanalyse wurde die folgende Kornverteilung ermittelt (> = größer als, < = kleiner als)

Figure imgb0001
A slurry which contained the abovementioned solids and 44.5% by weight of water and had a viscosity of 4,500 mpa · s at a processing temperature of 63 ° C. was sprayed into a drying tower at a pressure of 40 bar via nozzles. The counter-current dry gas had a temperature of 240 ° C in the ring channel and 120 ° C in the area of the tower outlet. The spray product was extremely free-flowing and had a bulk density of 450 g / l. The following particle size distribution was determined by sieve analysis (> = greater than, <= less than)
Figure imgb0001

Der Staubanteil (< 0,05 mm) lag unter 0,02 Gew.-%. Die Wasser­bindung betrug 0,6 Mol Wasser pro Mol Natriumcarbonat.The dust content (<0.05 mm) was less than 0.02% by weight. The water binding was 0.6 moles of water per mole of sodium carbonate.

2. Hie in Beispiel 1 beschrieben, wurde ein rieselfähiges, lager­beständiges Granulat folgender Zusammensetzung durch Sprüh­trocknung hergestellt:
50,0 Gew.-% Na-Salz des Acrylsäure-Maleinsäure-Copolymers,
40,8 Gew. -% Natriumcarbonat,
5,0 Gew. -% Natriumsulfat,
4,2 Gew.-% Hasser.2. As described in Example 1, a free-flowing, storage-stable granulate of the following composition was produced by spray drying:
50.0% by weight Na salt of the acrylic acid-maleic acid copolymer,
40.8% by weight sodium carbonate,
5.0% by weight sodium sulfate,
4.2% by weight haters.

Produktionsbedingungen: Wassergehalt des Slurries 45 Gew.-96, Slurry-Temperatur 64 °C, Viskosität 4 400 mpa·s, Sprühdruck 45 bar, Trockengastemperatur Eingang 270 °C, Ausgang 118 °C, Has­serbindung 0,59 mol H₂O pro Mol Natriumcarbonat. Das Schütt­gewicht betrug 440 g/l.
Siebanalyse:

Figure imgb0002
Production conditions: water content of the slurry 45% by weight, slurry temperature 64 ° C, viscosity 4,400 mpa · s, spray pressure 45 bar, dry gas temperature inlet 270 ° C, outlet 118 ° C, hater binding 0.59 mol H₂O per mol sodium carbonate. The bulk density was 440 g / l.
Sieve analysis:
Figure imgb0002

Der Staubanteil lag unter 0,02 Gew.-%. Das Sprühprodukt zeigte eine gleich gute Rieselfähigkeit wie das Produkt gemäß Beispiel 1, jedoch nahm sie im Verlauf einer mehrwöchigen Lagerung geringfügig ab. Das Produkt eignet sich daher insbesondere als Zumischkomponente zu granularen Reini­gungsmitteln bzw. zur Weiterverarbeitung zu granularen Ge­schirrspülmitteln, wobei diese geringe, sich erst nach längerer Lagerung ausbildende Tendenz zur verringerten Rieselfähigkeit nicht mehr auftrat.The dust content was less than 0.02% by weight. The spray product showed an equally good flowability as the product according to Example 1, but it decreased slightly over a period of several weeks. The product is therefore particularly suitable as an admixture component for granular detergents or for further processing into granular dishwashing detergents, this small tendency toward reduced free-flowing ability, which only develops after long storage, no longer occurs.

VergleichsversucheComparative tests

Wie im vorstehenden Beispiel 1 beschrieben, wurda Sprühprodukte der folgenden Zusammensetzung hergestellt (in Gew.-%):

  • A) 50,0 % Na-Salz des Acrylsäure-Maleinsäure-Copolymers,
    45,3 % Natriumcarbonat,
    4,7 % Wasser.
  • B) 30,0 % Na-Salz des Copolymers,
    54,8 % Natriumcarbonat,
    5,0 96 Natriumsulfat,
    10,2 % Wasser (Hasserbindung 1,07 Mol pro Mol Natriumcarbonat):
As described in Example 1 above, spray products of the following composition were prepared (in% by weight):
  • A) 50.0% Na salt of the acrylic acid-maleic acid copolymer,
    45.3% sodium carbonate,
    4.7% water.
  • B) 30.0% Na salt of the copolymer,
    54.8% sodium carbonate,
    5.0 96 sodium sulfate,
    10.2% water (hater bond 1.07 mol per mol sodium carbonate):

In Versuch A wurden die gleichen Sprühbedingungen angewandt wie im Beispiel 1 beschrieben, im Versuch B lag die Turmaustritts-Tempe­ratur der Trockengase bei 90 °C. Beide Sprühprodukte bestanden aus klebrigen, bereits unter leichtem Druck verformbaren Körnern. Das Rieselverhalten war unbefriedigend und bei dem Versuch, die Pro­dukte zusammen mit weiteren Reinigungsmittelbestandteilen zu sta­bilen Granulaten weiterzuverarbeiten, traten Störungen infolge Anklebungen an den Mischorganen und der Innenwand des Granulier­mischers auf.In experiment A, the same spray conditions were used as described in example 1, in experiment B the tower outlet temperature of the dry gases was 90 ° C. Both spray products consisted of sticky grains that could already be deformed under slight pressure. The flow behavior was unsatisfactory and when trying to process the products together with other detergent components into stable granules, problems occurred due to sticking to the mixing elements and the inner wall of the granulating mixer.

Claims (10)

1. Granulares, alkalisches, phosphatfreies Reinigungsadditiv ent­haltend im wesentlichen (a) 35 bis 60 Gew. -% an Natriumsalzen mindestens einer homopolymeren bzw. copolymeren (Meth-)Acrylsäure, (b) 25 bis 50 Gew.-% Natriumcarbonat (wasserfrei gerechnet), (c) 4 bis 20 Gew.-% Natriumsulfat (wasserfrei gerechnet), (d) 1 bis 7 Gew. -% Wasser. 1. Contains essentially granular, alkaline, phosphate-free cleaning additive (a) 35 to 60% by weight of sodium salts of at least one homopolymeric or copolymeric (meth) acrylic acid, (b) 25 to 50% by weight of sodium carbonate (calculated as anhydrous), (c) 4 to 20% by weight of sodium sulfate (calculated as anhydrous), (d) 1 to 7% by weight of water. 2. Mittel nach Anspruch 1, gekennzeichnet durch einen Gehalt an
40 bis 55 Gew.-% der Komponente (a),
30 bis 45 Gew.-96 der Komponente (b),
5 bis 15 Gew.-96 der Komponente (c),
2 bis 6 Gew.-96 der Komponente (d).2. Composition according to claim 1, characterized by a content of
40 to 55% by weight of component (a),
30 to 45 parts by weight of component (b),
5 to 15 parts by weight of component (c),
2 to 6 parts by weight of component (d). 3. Mittel nach Anspruch 1, gekennzeichnet durch einen Gehalt an
45 bis 52 Gew.-96 der Komponente (c),
30 bis 38 Gew.-% der Komponente (b),
5 bis 10 Gew.-96 der Komponente (c),
3 bis 5 Gew.-96 der Komponente (d).3. Composition according to claim 1, characterized by a content of
45 to 52% by weight of component (c),
30 to 38% by weight of component (b),
5 to 10 parts by weight of component (c),
3 to 5 parts by weight of component (d). 4. Mittel nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Komponente (a) aus den Natriumsalzen der Polyacrylsäure und/oder von Copolymeren aus 50 bis 90 Gew. -% Acrylsäure und 50 bis 10 Gew.-% Maloinsäure besteht.4. Composition according to one or more of claims 1 to 3, characterized in that component (a) from the sodium salts of polyacrylic acid and / or from copolymers of 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maloic acid consists. 5. Mittel nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Wassergehalt so bemessen ist, daß die Hasserbindung 0,3 bis 0,7 Mol H₂O pro Mol Natriumcarbonat be­trägt.5. Composition according to one or more of claims 1 to 4, characterized in that the water content is such that the hater bond is 0.3 to 0.7 moles of H₂O per mole of sodium carbonate. 6. Mittel nach einem oder mehreren der Ansprüche 1 bis 5, ge­kennzeichnet durch eine mittlere Korngröße 0,2 bis 1,2 mm, wobei der Anteil der Körner unterhalb 0,1 mm nicht mehr als 2 Gew.-% und oberhalb 2 mm nicht mehr als 20 Gew.-% beträgt.6. Composition according to one or more of claims 1 to 5, characterized by an average grain size 0.2 to 1.2 mm, the proportion of the grains below 0.1 mm not more than 2% by weight and above 2 mm not is more than 20% by weight. 7. Mittel nach Anspruch 6, in dem mindestens 80 Gew.-%, insbe­sondere mindestens 90 Gew.-% der Körner eine Größe von 0,2 bis 1,6 mm aufweisen, wobei der Anteil der Körner zwischen 0,1 und 0,05 mm nicht mehr als 3 Gew.-%, insbesondere nicht mehr als 1 Gew.-% und der Anteil der Körner zwischen 1,6 und 2,4 mm nicht mehr als 20 Gew.-%, insbesondere nicht mehr als 10 Gew.-% be­trägt.7. Composition according to claim 6, in which at least 80% by weight, in particular at least 90% by weight, of the grains have a size of 0.2 to 1.6 mm, the proportion of the grains being between 0.1 and 0, 05 mm not more than 3% by weight, in particular not more than 1% by weight and the proportion of the grains between 1.6 and 2.4 mm not more than 20% by weight, in particular not more than 10% by weight. -%. 8. Verfahren zur Herstellung des Mittels nach einem oder mehreren der Ansprüche 1 bis 7 durch Sprühtrocknungl dadurch gekenn­zeichnet, daß man einen Slurry, enthaltend 50 bis 68 Gew.-% an nichtwäßrigen Komponenten, versprüht und mit im Gegenstrom geführten Heizgasen trocknet, wobei die Temperatur des Trok­kengases im Bereich des Turmaustritts 100 bis 130 °C beträgt.8. A process for the preparation of the agent according to one or more of claims 1 to 7 by spray drying, characterized in that a slurry containing 50 to 68 wt .-% of non-aqueous components is sprayed and dried with countercurrent heating gases, the temperature of the dry gas in the area of the tower outlet is 100 to 130 ° C. 9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß das Heizgas in der Eingangszone des Turmes eine Temperatur von 200 bis 320 °C aufweist.9. The method according to claim 8, characterized in that the heating gas in the entrance zone of the tower has a temperature of 200 to 320 ° C. 10. Verwendung eines Mittels nach einem oder mehreren der Ansprü­che 1 bis 7 als Mischungsbestandteil oder Granulatkomponente in Wasch- und Reinigungsmitteln.10. Use of an agent according to one or more of claims 1 to 7 as a constituent of the mixture or granulate in detergents.
EP90121008A 1989-11-10 1990-11-02 Granular, alkaline and phosphate-free detergent additive Expired - Lifetime EP0432437B1 (en)

Applications Claiming Priority (2)

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DE3937469 1989-11-10
DE3937469A DE3937469A1 (en) 1989-11-10 1989-11-10 GRANULAR, ALKALINE, PHOSPHATE-FREE CLEANING ADDITIVE

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EP0432437A1 true EP0432437A1 (en) 1991-06-19
EP0432437B1 EP0432437B1 (en) 1995-10-11

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992018604A1 (en) * 1991-04-12 1992-10-29 Henkel Kommanditgesellschaft Auf Aktien Process for producing detergent tablets for dishwashing machines
WO1993000419A1 (en) * 1991-06-27 1993-01-07 Henkel Kommanditgesellschaft Auf Aktien Method for the production of cleaing-agent tablets for machine dishwashing
WO1993010210A1 (en) * 1991-11-14 1993-05-27 Henkel Kommanditgesellschaft Auf Aktien Method of manufacturing dense-granulate low-alkali washing agents, containing no active chlorine or phosphate, for washing-up machines
ES2070736A1 (en) * 1992-04-21 1995-06-01 Henkel Kgaa Stable, free-flowing granulate of alkaline cleaning additive - contg. (meth)acrylic] acid (co)polymer, sodium silicate, sodium carbonate or sodium sulphate, sequestering agent and water
WO2006020790A1 (en) * 2004-08-11 2006-02-23 The Procter & Gamble Company Process for making a granular detergent composition having improved solubility

Families Citing this family (7)

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DE4110510A1 (en) * 1991-03-30 1992-10-01 Henkel Kgaa LOW-ALKALINE, CHLORINE AND PHOSPHATE-FREE MACHINE DISTRIBUTORS IN THE FORM OF HEAVY-DENTAL POWDERS AND GRANULES
EP0626996A1 (en) * 1992-02-20 1994-12-07 Henkel Kommanditgesellschaft auf Aktien Process for producing low-alkaline dishwasher rinsing agents without active chlorine, silicates and phosphates, in the form of heavy granulates
US5898025A (en) * 1992-09-25 1999-04-27 Henkel Kommanditgesellschaft Auf Aktien Mildly alkaline dishwashing detergents
DE4315048A1 (en) * 1993-04-01 1994-10-06 Henkel Kgaa Process for the production of stable, bifunctional, phosphate, metasilicate and polymer-free, low-alkaline detergent tablets for automatic dishwashing
CA2175329C (en) * 1993-11-03 2000-01-18 Eugene Steven Sadlowski Control of calcium carbonate precipitation in automatic dishwashing
DE4408718A1 (en) * 1994-03-15 1995-09-21 Henkel Kgaa Breakage and storage stable, polyfunctional cleaning tablets, process for their preparation and their use
US6150324A (en) 1997-01-13 2000-11-21 Ecolab, Inc. Alkaline detergent containing mixed organic and inorganic sequestrants resulting in improved soil removal

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US4399048A (en) * 1977-10-06 1983-08-16 Colgate-Palmolive Company High bulk density particulate heavy duty laundry detergent
EP0221776A2 (en) * 1985-11-01 1987-05-13 Unilever Plc Detergent compositions, components therefor, and processes for their preparation
EP0243908A2 (en) * 1986-05-02 1987-11-04 Henkel Kommanditgesellschaft auf Aktien Granular, phosphate-free water-softening agent

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US3933673A (en) * 1970-01-08 1976-01-20 Lever Brothers Company Detergent compositions containing polymeric builders
US4399048A (en) * 1977-10-06 1983-08-16 Colgate-Palmolive Company High bulk density particulate heavy duty laundry detergent
EP0221776A2 (en) * 1985-11-01 1987-05-13 Unilever Plc Detergent compositions, components therefor, and processes for their preparation
EP0243908A2 (en) * 1986-05-02 1987-11-04 Henkel Kommanditgesellschaft auf Aktien Granular, phosphate-free water-softening agent

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992018604A1 (en) * 1991-04-12 1992-10-29 Henkel Kommanditgesellschaft Auf Aktien Process for producing detergent tablets for dishwashing machines
US5358655A (en) * 1991-04-12 1994-10-25 Henkel Kommanditgesellschaft Auf Aktien Process for the production of detergent tablets for dishwashing machines
WO1993000419A1 (en) * 1991-06-27 1993-01-07 Henkel Kommanditgesellschaft Auf Aktien Method for the production of cleaing-agent tablets for machine dishwashing
WO1993010210A1 (en) * 1991-11-14 1993-05-27 Henkel Kommanditgesellschaft Auf Aktien Method of manufacturing dense-granulate low-alkali washing agents, containing no active chlorine or phosphate, for washing-up machines
ES2070736A1 (en) * 1992-04-21 1995-06-01 Henkel Kgaa Stable, free-flowing granulate of alkaline cleaning additive - contg. (meth)acrylic] acid (co)polymer, sodium silicate, sodium carbonate or sodium sulphate, sequestering agent and water
WO2006020790A1 (en) * 2004-08-11 2006-02-23 The Procter & Gamble Company Process for making a granular detergent composition having improved solubility
US7459422B2 (en) 2004-08-11 2008-12-02 The Procter & Gamble Company Process for making a granular detergent composition having improved solubility

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ATE129008T1 (en) 1995-10-15
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ES2077619T3 (en) 1995-12-01
DE59009767D1 (en) 1995-11-16

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