EP0571436A1 - Granular additive for washing and cleaning agents. - Google Patents

Granular additive for washing and cleaning agents.

Info

Publication number
EP0571436A1
EP0571436A1 EP92904218A EP92904218A EP0571436A1 EP 0571436 A1 EP0571436 A1 EP 0571436A1 EP 92904218 A EP92904218 A EP 92904218A EP 92904218 A EP92904218 A EP 92904218A EP 0571436 A1 EP0571436 A1 EP 0571436A1
Authority
EP
European Patent Office
Prior art keywords
weight
water
granules
spray
additive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP92904218A
Other languages
German (de)
French (fr)
Other versions
EP0571436B1 (en
Inventor
Lothar Pioch
Wolfgang Seiter
Otto Koch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0571436A1 publication Critical patent/EP0571436A1/en
Application granted granted Critical
Publication of EP0571436B1 publication Critical patent/EP0571436B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • 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 invention relates to a granular additive for detergents and cleaners and to a process for the preparation of these additives.
  • the additives are usually stored separately from granular detergents and cleaning agents and, depending on requirements, are used together with these in washing or cleaning processes. In the sense of an additional builder effect, they improve the cleaning ability of the actual washing and cleaning agent and prevent the formation of hard limescale deposits on the heating elements or on the textile fiber.
  • the detergents can be mixed with granular detergents or further processed together with them, whereby they have an advantageous influence on their pouring properties and rinsing behavior or enable trouble-free further processing.
  • Known agents of this type often contain salts of polymeric aliphatic carboxylic acids. These include in particular salts of polyacrylic acid and polymethacrylic acid and salts of 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 156% by weight of such polymer salts. Since the salts of the polymeric polycarboxylates are hygroscopic, mixtures with higher proportions of such salts cannot readily be converted into storage-stable and free-flowing granules, especially not if they do not contain any water-binding or water-repellent mixture components.
  • German patent application 21 00 500 proposes to use the polymers as free acids or partially neutralized salts with a maximum degree of neutralization of 60% or to convert them from their aqueous solutions into granular products by hot spray drying .
  • the polymeric carboxylic acids only develop their full effect as completely neutralized salts.
  • the alkaline agent required for neutralization must therefore be added to the acidic granules.
  • the invention relates to a granular additive that
  • Suitable homopolymers are sodium salts of polymethacrylic acid and preferably polyacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acids). If only homopolymeric polyacrylic acids (in salt form) are used, their relative molecular mass is preferably 1,000 to 80,000 (based on acid) in the interest of good flowability and storage stability.
  • Suitable copolymers are those of acrylic acid with methacrylic acid and preferably copolymers of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • 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.
  • Their relative molecular weight, based on free acids is generally from 5000 to 200,000, preferably from 10,000 to 120000 and in particular 50000 to 100000.
  • 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% by weight of 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 content of homopolymeric or copolymeric (meth) acrylates in the additives is preferably 45 to 65% by weight and in particular 50 to 62% by weight.
  • the fine crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality. It can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 1 -C 4 -alcohols with 2 to 5 Glycol ether groups. Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 20 to 22% by weight of bound water. The zeolite content of the additives is preferably 8 to 30% by weight and in particular 10 to 25% by weight.
  • the sodium sulfate is used in anhydrous form, preferably in amounts of 4 to 15% by weight and in particular 7 to 15% by weight.
  • zeolite When only small amounts of zeolite are used, for example from 3 to 10% by weight, it is advisable to choose a somewhat higher proportion of sodium sulfate, for example in the range from 8 to 15% by weight.
  • Sodium sulfate contents of more than 7% by weight, for example 8 to 15% by weight fundamentally improve the grain properties and the shelf life of the additives. It is very surprising that fractions of 5 to 6% by weight of sodium sulfate are sufficient to contain additives according to the invention with a content of about Stabilize 50 wt .-% of polymeric carboxylates and ensure good flow properties.
  • the water content of the additives which is not bound by the zeolite, is preferably not more than 12% by weight, based on the additive, and is in particular in the range from 3 to 11% by weight.
  • the additives can have sodium carbonate in anhydrous form in amounts of not more than 20% by weight. In a preferred embodiment, the additives contain 3 to 15% by weight and in particular 4 to 12% by weight of anhydrous sodium carbonate.
  • the additives can contain small amounts, for example 0.5 to 3% by weight, based on the additive, of surfactants, such as soap, sulfonates (for example dodecylbenzenesulfonate), organic sulfates (for example fatty alkyl sulfates) or alkypolyglycosides.
  • surfactants such as soap, sulfonates (for example dodecylbenzenesulfonate), organic sulfates (for example fatty alkyl sulfates) or alkypolyglycosides.
  • the additives can also contain small amounts of further constituents, such as dyes and color pigments, and can be colored uniformly or speckled.
  • the proportion of such components is in each case well below 1% by weight.
  • the average grain size of the granular additive is usually 0.2 to 1.2 mm, the proportion of the granules below 0.1 mm not more than 10% by weight and above 2 mm not more than 20% by weight (sieve analysis ⁇ se).
  • at least 75% by weight, in particular at least 85% by weight, of the granules have a size of 0.2 to 1.6 mm, the proportion of the granules having a grain size between 0.1 and 0.05 mm not more than 4% by weight, in particular not more than 3% by weight and the proportion of the grains between 1.6 and 2.4 mm not more than 20% by weight, preferably not more than 10% by weight and in particular is not more than 6% by weight. Larger proportions of fine grain generally lead to a deterioration in the induction behavior.
  • the granules can be produced, for example, by intensive mixing of the dry constituents with participation Liquids, in particular water, are carried out in conventional granulating devices. However, spray drying of an aqueous slurry is preferred.
  • the slurry concentration is preferably between 50 and 68% by weight (non-aqueous fraction) and in particular between 55 and 60% by weight, the viscosity of the paste being decisive, which should not exceed 10000 mPa-s and advantageously 2500 to 6000 mPa * s is. (The viscosity is measured in the low-pressure part of the spray tower at temperatures between 60 and 100 ° C. using a truncated cone viscometer). 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 90 and 130 ° C, preferably between 100 and 125 ° C.
  • Such comparatively high operating temperatures are advantageous for the production of a perfect product and, despite the high proportion of organic substance in the spray product, are not critical, since the self-ignition temperature is above 330 ° C., usually even above 350 ° C.
  • Conventional spray drying systems spray nozzles or spray disks can be used for spray drying, the spray nozzles being able 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 washing machines and dishwashers without leaving any residue and retain these advantageous properties even after a long storage period.
  • the granules according to the invention usually have a bulk density of 240 to 450 g / 1, usually one of 320 to 400 g / 1. If small amounts, for example 0.5 to 3% by weight, of surfactants, such as soaps, sulfonates, organic sulfates or alkylpolyglycosides, were added to the granules before the spray drying, the bulk density may be 50 to 150 g / l lower than without this addition. In a further and preferred embodiment, granules with a higher bulk density, in particular those of 500 to 900 g / 1, are claimed.
  • surfactants such as soaps, sulfonates, organic sulfates or alkylpolyglycosides
  • the bulk density can be increased in a manner known per se by compacting the light granules, for which purpose in principle all techniques are suitable which are carried out under pressure and, if appropriate, with the addition of a small amount of liquid, for example by roller compaction, pelleting, extrusion or tableting.
  • a small amount of liquid for example by roller compaction, pelleting, extrusion or tableting.
  • pressing by means of rollers for example at a pressure between 100 and 200 bar, is preferred. Since the spray-dried granules have a certain plasticity under pressure, a flake-shaped product can be obtained in this way, which can then, if necessary, be comminuted to the desired particle size.
  • the compacted products surprisingly retain their good dispersing and dissolving properties.
  • the bulk density of such products is in particular between 650 and 800 g / l.
  • liquid binders preferably water and / or nonionic, in particular ethoxylated, nonionic surfactants, paste-like anionic surfactants and paraffin oil can be added to the granular additives.
  • binder the content of which, based on the compacted granulate, advantageously does not exceed 10% by weight, preferably 2 to 8% by weight and in particular 3 to 6% by weight, improves the plasticizability of the light additive and the density of the compacted additive increases.
  • the binders can be mixed with the light additive or sprayed onto the light granulate, for example by spraying the powder stream fed to the roller with water or aqueous surfactant solutions. If water is selected as the binder, water can be omitted if the granules obtained, for example, by spray drying have not been completely dried, so that a residual moisture, for example 6 to 15% by weight of water, is retained in the spray-dried granules. The further processing of such slightly moist spray granules is a preferred method of operation.
  • the compacting can also be carried out in a screw press or in a granulating device after the addition of appropriate amounts of liquid. Subsequent post-drying of the compacted additives is generally not necessary and, in particular, is also not preferred.
  • the active ingredient content of the non-dried compacts slightly decreases according to the amount of liquid added.
  • the compacted granules are also free-flowing and their storage stability under unfavorable conditions, for example in a moist atmosphere, also exceeds the spray-dried products.
  • a granular additive of the composition (in% by weight)
  • a slurry heated to 77 ° C which contained the aforementioned solids and 47.0 wt .-% water and had a viscosity of 2500 mPa-s (60 ° C; truncated cone viscometer from Brabender, Duisburg, Federal Republic of Germany), was with a Pressure of 40 bar sprayed through nozzles in a drying tower.
  • the counter-current dry gas had a temperature of 210 ° 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 320 g / l.
  • the following particle size distribution was determined by sieve analysis (> greater than, ⁇ less than)
  • the dust content ( ⁇ 0.05 mm) was less than 0.02% by weight.
  • the product proved to be stable in storage and quickly and completely redispersible in cold water.
  • the parts with a grain size of more than 1.6 mm and less than 0.1 mm were separated off by sieving.
  • 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, 20.0% by weight zeolite NaA, spray-dried, 10.0% by weight sodium sulfate (anhydrous), 9.0% by weight sodium carbonate ( anhydrous), 11.0% by weight water.
  • 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.
  • APG stands for an alkyl polyglucoside, derived from linear ones and with an average degree of oligomerization of the glucose residue of 1.4.
  • the product made with this addition draws is characterized by an above-average degree of whiteness and a comparatively low bulk density.
  • the product according to Example 3 requires a somewhat lower product throughput per unit of time in the drying tower because of its somewhat difficult drying properties. All granules were free-flowing and stable in storage and proved to be completely and quickly redispersible when introduced into cold tap water.
  • spray products of the following composition were produced (in% by weight):
  • experiment A the same spraying 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 which could already be deformed under slight pressure. The flow behavior was unsatisfactory and when trying to process the products together with other cleaning constituents into stable granules, problems occurred due to sticking to the mixing element and the inner wall of the granulating mixer.
  • the granules according to Example 1 • and 2 were fed to a roller compactor.
  • the roller pressure was 150 bar.
  • the lower-water granules were sprayed with 4% by weight of water before the pressing, while the more water-rich product was compacted according to Example 2.
  • the pressed material was continuously in one Hammer basket grinder crushed.
  • Granules with a grain size greater than 1.6 mm and less than 0.2 mm were sieved.
  • the screened fine and coarse fractions were fed back into the powder stream to be compacted.
  • the result was hard-grained, easily pourable, abrasion-resistant splinter granules with the following powder specifications.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
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Abstract

The granular additive disclosed, which may be used to pretreat hard water or employed together with washing and cleaning agents, contains 40-75 % by wt. of the sodium salts of at least one homopolymer or copolymer of methacrylic acid, 1-35 % by wt. of a finely crystalline synthetic zeolite containing bound water, 2-20 % by wt. of sodium sulphate (calculated as the anhydrous salt) and 1-15 % by wt. of water. The granulate initially produced preferably by spray drying is compacted under the action of pressure to give a granulate with a bulk density between 500 and 900 g/l, without affecting the free-running or storage characteristics of the granulate.

Description

"Granuläres Additiv für Wasch- und Reinigungsmittel" "Granular additive for detergents and cleaning agents"
Die Erfindung betrifft ein granuläres Additiv für Wasch- und Reinigungs¬ mittel sowie ein Verfahren zur Herstellung dieser Additive.The invention relates to a granular additive for detergents and cleaners and to a process for the preparation of these additives.
Aufgrund seiner guten Kalkbindungseigenschaften kann es als Zusatz zur Waschlauge in Hartwassergebieten oder zur Vorbehandlung von hartem, für Wasch-, Spül- und Reinigungszwecke bestimmtem Wasser verwendet werden. Die Additive werden üblicherweise separat von granulären Wasch- und Reini¬ gungsmitteln aufbewahrt und, je nach Bedarf, zusammen mit diesen in Wasch¬ oder Reinigungsprozessen eingesetzt. Sie verbessern im Sinne einer zu¬ sätzlichen Builderwirkung das Reinigungsvermögen des eigentlichen Wasch- und Reinigungsmittels und verhindern die Ausbildung harter Kalknieder¬ schläge auf den Heizelementen bzw. auf der Textilfaser. Die Mittel können in besonderen Fällen granulären Wasch- und Reinigungsmitteln zugemischt oder mit diesen zusammen weiterverarbeitet werden, wobei sie deren Rieseleigenschaften und Einspülverhalten vorteilhaft beeinflussen bzw. eine störungsfreie Weiterverarbeitung ermöglichen.Due to its good lime binding properties, it can be used as an additive to wash water in hard water areas or for the pretreatment of hard water intended for washing, rinsing and cleaning purposes. The additives are usually stored separately from granular detergents and cleaning agents and, depending on requirements, are used together with these in washing or cleaning processes. In the sense of an additional builder effect, they improve the cleaning ability of the actual washing 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 mixed with granular detergents or further processed together with them, whereby they have an advantageous influence on their pouring properties and rinsing behavior or enable trouble-free further processing.
Bekannte Mittel dieser Art enthalten oft Salze polymerer aliphatischer Carbonsäuren. Hierzu zählen insbesondere Salze der Polyacrylsäure und Po- lymethacrylsäure sowie Salze von Copolymeren dieser beiden Säuren mit Maleinsäure und/oder Vinylestern. Es bereitet keine Schwierigkeiten, la¬ gerbeständige Granulate herzustellen, die bis zu ca. 156ew.-% derartiger Polymersalze enthalten. Da die Salze der polymeren Polycarboxylate hygro¬ skopisch sind, lassen sich jedoch Mischungen mit höheren Anteilen an sol¬ chen Salzen nicht ohne weiteres in lagerstabile und rieselfähige Granulate überführen, insbesondere dann nicht, wenn sie keine wasserbindenden oder wasserabweisenden Mischungsbestandteile enthalten.Known agents of this type often contain salts of polymeric aliphatic carboxylic acids. These include in particular salts of polyacrylic acid and polymethacrylic acid and salts of 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 156% by weight of such polymer salts. Since the salts of the polymeric polycarboxylates are hygroscopic, mixtures with higher proportions of such salts cannot readily be converted into storage-stable and free-flowing granules, especially not if they do not contain any water-binding or water-repellent mixture components.
In der deutschen Patentanmeldung 21 00 500 (Unilever) wird zur Lösung dieses Problems vorgeschlagen, die Polymeren als freie Säuren oder teil¬ neutralisierte Salze mit einem Neutralisationsgrad von maximal 60% einzu¬ setzen bzw. aus ihren wäßrigen Lösungen durch Heißsprühtrocknen in körnige Produkte zu überführen. Mittel, die einen höheren Anteil an neutralisier¬ ten Salzen enthielten, zeigten schon nach einwöchiger Lagerung unter Raumtemperaturbedingungen eine starke Erweichung. Jedoch entfalten die poly eren Carbonsäuren ihre volle Wirkung nur als vollständig neutrali¬ sierte Salze. Das zur Neutral sation benötigte alkalische Mittel muß daher den sauren Granulaten nachträglich zugemischt werden.To solve this problem, German patent application 21 00 500 (Unilever) proposes to use the polymers as free acids or partially neutralized salts with a maximum degree of neutralization of 60% or to convert them from their aqueous solutions into granular products by hot spray drying . Agents that contained a higher proportion of neutralized salts already showed after storage for one week Room temperature conditions a strong softening. However, the polymeric carboxylic acids only develop their full effect as completely neutralized salts. The alkaline agent required for neutralization must therefore be added to the acidic granules.
Es wurde nun überraschenderweise gefunden, daß definierte Salzgemische mit einem vergleichsweise hohen Gehalt an vollständig neutralisierten Salzen polymerer Carbonsäuren hergestellt werden können, die als Granulate lagerbeständig und gut rieselfähig sind.It has now surprisingly been found that defined salt mixtures can be produced with a comparatively high content of completely neutralized salts of polymeric carboxylic acids which are storage-stable and free-flowing as granules.
Gegenstand der Erfindung ist ein granuläres Additiv, dasThe invention relates to a granular additive that
40 bis 75 Gew.-% an Natriumsalzen mindestens einer homopolymeren bzw. co- polymeren (Meth-)Acrylsäure,40 to 75% by weight of sodium salts of at least one homopolymeric or copolymeric (meth) acrylic acid,
1 bis 35 Gew.-% an- synthetischem, feinkristallinem, gebundenes Wasser enthaltenden Zeolith,1 to 35% by weight of synthetic, finely crystalline, bound water-containing zeolite,
2 bis 20 Gew.-% Natriumsulfat (wasserfrei gerechnet) und 1 bis 15 Gew.-% Wasser enthält.Contains 2 to 20 wt .-% sodium sulfate (calculated anhydrous) and 1 to 15 wt .-% water.
Geeignete Homopolymere sind Natriumsalze der Polymethacrylsäure und be¬ vorzugt der Polyacrylsäure, beispielsweise solche mit einer relativen Mo¬ lekülmasse von 800 bis 150000 (auf Säuren bezogen). Werden ausschließlich homopolymere Polyacrylsäuren (in Salzform) verwendet, beträgt deren rela¬ tive Molekülmasse im Interesse einer guten Rieselfähigkeit und Lagerbe¬ ständigkeit vorzugsweise 1 000 bis 80000 (auf Säure bezogen).Suitable homopolymers are sodium salts of polymethacrylic acid and preferably polyacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acids). If only homopolymeric polyacrylic acids (in salt form) are used, their relative molecular mass 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 Copolymere der Acrylsäure oder Methacrylsäure mit Maleinsäu¬ re. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Ma¬ leinsäure erwiesen, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Besonders bevorzugt sind solche Copolymere, in de¬ nen 60 bis 85 Gew.-% Acrylsäure und 40 bis 15 Gew.-% Maleinsäure vorlie¬ gen. Ihre relative Molekülmasse, bezogen auf freie Säuren, beträgt im allgemeinen 5000 bis 200000, vorzugsweise 10000 bis 120000 und insbe¬ sondere 50000 bis 100000. Mit Vorteil lassen sich auch Gemische verschiedener Homo- und Copolymerer einsetzen, insbesondere Gemische aus homopoly erer Acrylsäure und den vorstehend beschriebenen Copolymeren aus 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% 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 al¬ leinigem Einsatz etwas mehr zum Kleben bzw. Zerfließen der Körner neigen als niedermolekulare Polyacrylate.Suitable copolymers are those of acrylic acid with methacrylic acid and preferably copolymers of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. 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. Their relative molecular weight, based on free acids, is generally from 5000 to 200,000, preferably from 10,000 to 120000 and in particular 50000 to 100000. 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% by weight of 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.
Der Gehalt der Additive an homopolymeren oder copolymeren (Meth-)Acrylaten beträgt vorzugsweise 45 bis 65 Gew.-% und insbesondere 50 bis 62 Gew.-%.The content of homopolymeric or copolymeric (meth) acrylates in the additives is preferably 45 to 65% by weight and in particular 50 to 62% by weight.
Der eingesetzte feinkristalline, synthetische und gebundenes Wasser ent¬ haltende Zeolith ist vorzugsweise Zeolith NaA in Waschmittelqualität. Er kann als sprühgetrocknetes Pulver oder auch als ungetrocknete, von ihrer Herstellung noch feuchte, stabilisierte Suspension zum Einsatz kommen. Für den Fall, daß der Zeolith als Suspension eingesetzt wird, kann diese ge¬ ringe Zusätze an nichtionischen Tensiden als Stabilisatoren enthalten, beispielsweise 1 bis 3 Gew.-%, bezogen auf Zeolith, an ethoxylierten C^-Cig-Alkoholen mit 2 bis 5 Glykolethergruppen. Geeignete Zeolithe wei¬ sen eine mittlere Teilchengröße von weniger als 10 μm (Volumenverteilung; Meßmethode: Coulter Counter) auf und enthalten vorzugsweise 20 bis 22 Gew.-% an gebundenem Wasser. Der Gehalt der Additive an Zeolith beträgt vorzugsweise 8 bis 30 Gew.-% und insbesondere 10 bis 25 Gew.-%.The fine crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality. It can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 1 -C 4 -alcohols with 2 to 5 Glycol ether groups. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 20 to 22% by weight of bound water. The zeolite content of the additives is preferably 8 to 30% by weight and in particular 10 to 25% by weight.
Das Natriumsulfat wird in wasserfreier Form vorzugsweise in Mengen von 4 bis 15 Gew.-% und insbesondere von 7 bis 15 Gew.-% eingesetzt. Beim Ein¬ satz nur geringer Mengen an Zeolith, beispielsweise von 3 bis 10 Gew.-%, empfiehlt es sich, den Anteil an Natriumsulfat etwas höher zu wählen, beispielsweise im Bereich von 8 bis 15 Gew.-%. Anteile an Natriumsulfat von über 7 Gew.-%, beispielsweise 8 bis 15 Gew.-%, verbessern grundsätz¬ lich die Korneigenschaften und die Lagerbeständigkeit der Additive. Es ist sehr überraschend, daß bereits Anteile von 5 bis 6 Gew.-% an Natriumsulfat ausreichen, um erfindungsgemäße Additive mit einem Gehalt von etwa 50 Gew.-% an polymeren Carboxylaten zu stabilisieren und gute Rieseleigenschaften zu gewährleisten.The sodium sulfate is used in anhydrous form, preferably in amounts of 4 to 15% by weight and in particular 7 to 15% by weight. When only small amounts of zeolite are used, for example from 3 to 10% by weight, it is advisable to choose a somewhat higher proportion of sodium sulfate, for example in the range from 8 to 15% by weight. Sodium sulfate contents of more than 7% by weight, for example 8 to 15% by weight, fundamentally improve the grain properties and the shelf life of the additives. It is very surprising that fractions of 5 to 6% by weight of sodium sulfate are sufficient to contain additives according to the invention with a content of about Stabilize 50 wt .-% of polymeric carboxylates and ensure good flow properties.
Der Gehalt der Additive an Wasser, das nicht durch den Zeolith gebunden wird, beträgt vorzugsweise nicht mehr als 12 Gew.-%, bezogen auf das Ad¬ ditiv, und liegt insbesondere im Bereich von 3 bis 11 Gew.-%.The water content of the additives, which is not bound by the zeolite, is preferably not more than 12% by weight, based on the additive, and is in particular in the range from 3 to 11% by weight.
Zusätzlich können die Additive Natriumcarbonat in wasserfreier Form in Mengen nicht über 20 Gew.-% aufweisen. In einer bevorzugten Ausführungs¬ form enthalten die Additive 3 bis 15 Gew.-% und insbesondere 4 bis 12 Gew.-% an wasserfreiem Natriumcarbonat.In addition, the additives can have sodium carbonate in anhydrous form in amounts of not more than 20% by weight. In a preferred embodiment, the additives contain 3 to 15% by weight and in particular 4 to 12% by weight of anhydrous sodium carbonate.
Sofern erwünscht, können die Additive geringe Anteile, beispielsweise 0,5 bis 3 Gew.-%, bezogen auf das Additiv, an Tensiden, wie Seife, Sulfonate (beispielsweise Dodecylbenzolsulfonat), organische Sulfate (beispielsweise Fettalkylsulfate) oder Alkypolyglykoside enthalten.If desired, the additives can contain small amounts, for example 0.5 to 3% by weight, based on the additive, of surfactants, such as soap, sulfonates (for example dodecylbenzenesulfonate), organic sulfates (for example fatty alkyl sulfates) or alkypolyglycosides.
Weiterhin können die Additive noch geringe Mengen an weiteren Bestandtei¬ len, wie Farbstoffe und Farbpigmente, enthalten und einheitlich oder ge¬ sprenkelt angefärbt sein. Der Anteil derartiger Bestandteile liegt jeweils deutlich unter 1 Gew.-%.Furthermore, the additives can also contain small amounts of further constituents, such as dyes and color pigments, and can be colored uniformly or speckled. The proportion of such components is in each case well below 1% by weight.
Die mittlere Korngröße des granulären Additivs beträgt üblicherweise 0,2 bis 1,2 mm, wobei der Anteil der Granulate unterhalb 0,1 mm nicht mehr als 10 Gew.-% und oberhalb 2 mm nicht mehr als 20 Gew.-% beträgt (Siebanaly¬ se). Vorzugsweise weisen mindestens 75 Gew.-%, insbesondere mindestens 85 Gew.-% der Granulate eine Größe von 0,2 bis 1,6 mm auf, wobei der An¬ teil der Granulate mit einer Korngröße zwischen 0,1 und 0,05 mm nicht mehr als 4 Gew.-%, insbesondere nicht mehr als 3 Gew.-% und der Anteil der Körner zwischen 1,6 und 2,4 mm nicht mehr als 20 Gew.-%, vorzugsweise nicht mehr als 10 Gew.-% und insbesondere nicht mehr als 6 Gew.-% beträgt. Größere Anteile an Feinkorn führen in der Regel zu einer Verschlechterung des Einspülverhalteπs.The average grain size of the granular additive is usually 0.2 to 1.2 mm, the proportion of the granules below 0.1 mm not more than 10% by weight and above 2 mm not more than 20% by weight (sieve analysis ¬ se). Preferably, at least 75% by weight, in particular at least 85% by weight, of the granules have a size of 0.2 to 1.6 mm, the proportion of the granules having a grain size between 0.1 and 0.05 mm not more than 4% by weight, in particular not more than 3% by weight and the proportion of the grains between 1.6 and 2.4 mm not more than 20% by weight, preferably not more than 10% by weight and in particular is not more than 6% by weight. Larger proportions of fine grain generally lead to a deterioration in the induction behavior.
Die Herstellung der Granulate kann beispielsweise durch intensive Vermi¬ schung der trockenen Bestandteile unter Beteiligung geringer Flüssigkeitsmengen, insbesondere von Wasser, in üblichen Granuliervor¬ richtungen erfolgen. Bevorzugt ist jedoch die Sprühtrocknung eines wä߬ rigen Slurries. Dabei liegt die Slurrykonzentration vorzugsweise zwischen 50 und 68 Gew.-% (nichtwäßriger Anteil) und insbesondere zwischen 55 und 60 Gew.-%, wobei die Viskosität der Paste maßgebend ist, die 10000 mPa-s nicht überschreiten sollte und vorteilhafterweise 2500 bis 6000 mPa*s beträgt. (Die Messung der Viskosität erfolgt im Niederdruckteil des Sprühturms bei Temperaturen zwischen 60 und 100 °C mittels eines Kegel¬ stumpf-Viskosimeters). 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 Gegen¬ strom geführten Trockengase in der Eingangszone des Sprühturms, d.h. im sogenannten Ringkanal, liegt vorteilhafterweise zwischen 200 und 320 °C, insbesondere zwischen 220 und 300 °C. Im Bereich des Turmaustritts soll sie zwischen 90 und 130 °C, vorzugsweise zwischen 100 und 125 °C liegen. Derart vergleichsweise hohe Betriebstemperaturen sind für die Herstellung eines einwandfreien Produktes von Vorteil und trotz des hohen Anteils an organischer Substanz im Sprühprodukt nicht kritisch, da die Selbstentzün¬ dungstemperatur oberhalb 330 °C, meist sogar oberhalb 350 °C liegt. Zur Sprühtrocknung können übliche Sprühtrocknungsanlagen (Sprühtürme) mit Sprühdüsen oder Sprühscheiben eingesetzt werden, wobei die Sprühdüsen in einer oder mehreren Ebenen angeordnet sein können.The granules can be produced, for example, by intensive mixing of the dry constituents with participation Liquids, in particular water, are carried out in conventional granulating devices. However, spray drying of an aqueous slurry is preferred. The slurry concentration is preferably between 50 and 68% by weight (non-aqueous fraction) and in particular between 55 and 60% by weight, the viscosity of the paste being decisive, which should not exceed 10000 mPa-s and advantageously 2500 to 6000 mPa * s is. (The viscosity is measured in the low-pressure part of the spray tower at temperatures between 60 and 100 ° C. using a truncated cone viscometer). 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 90 and 130 ° C, preferably between 100 and 125 ° C. Such comparatively high operating temperatures are advantageous for the production of a perfect product and, despite the high proportion of organic substance in the spray product, are not critical, since the self-ignition temperature is above 330 ° C., usually even above 350 ° C. Conventional spray drying systems (spray towers) with spray nozzles or spray disks can be used for spray drying, the spray nozzles being able 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 Wasch- 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 washing machines and dishwashers without leaving any residue and retain these advantageous properties even after a long storage period.
Die erfindungsgemäßen Granulate weisen üblicherweise ein Schüttgewicht von 240 bis 450 g/1, meist ein solches von 320 bis 400 g/1 auf. Sofern den Granulaten geringe Anteile, beispielsweise 0,5 bis 3 Gew.-%, an Tensiden, wie Seifen, Sulfonaten, organischen Sulfaten oder Alkylpolyglykosiden vor der Sprühtrocknung zugesetzt wurden, kann das Schüttgewicht dadurch um Beträge von 50 bis 150 g/1 niedriger ausfallen als ohne diesen Zusatz. In einer weiteren und bevorzugten Ausführungsform werden Granulate mit einem höheren Schüttgewicht, insbesondere einem solchen von 500 bis 900 g/1 beansprucht. Eine Erhöhung des Schüttgewichtes kann in an sich bekannter Weise durch Kompaktieren des leichten Granulats erfolgen, wozu prinzipiell alle Techniken geeignet sind, die unter Druck und gegebenen¬ falls unter Zugabe einer geringen Flüssigkeits enge durchgeführt werden, beispielsweise durch Walzenkompaktierung, Pelletierung, Extrusion oder Tablettierung. Bei der Kompaktierung sprühgetrockneter Additive ist das Verpressen mittels Walzen, beispielsweise bei einem Druck zwischen 100 und 200 bar, bevorzugt. Da die sprühgetrockneten Granulate unter Druck eine gewisse Plastizität besitzen, läßt sich auf diese Weise ein schuppenför- miges Produkt erzielen, das gegebenenfalls noch anschließend auf die ge¬ wünschte PartikelgröBe zerkleinert werden kann. Die verdichteten Produkte behalten überraschenderweise ihre guten Dispergier- und Lösungseigen¬ schaften bei. Das Schüttgewicht liegt bei derartigen Produkten insbeson¬ dere zwischen 650 und 800 g/1. Vor bzw. während der Verdichtung können den granulären Additiven flüssige Bindemittel, vorzugsweise Wasser und/oder nichtionische, insbesondere ethoxylierte nichtionische Tenside, pasten- förmige Aniontenside sowie Paraffinöl zugesetzt werden. Durch den Zusatz an Bindemittel, dessen Gehalt, bezogen auf das kompaktierte Granulat, zweckmäßigerweise nicht über 10 Gew.-% , vorzugsweise 2 bis 8 Gew.-% und insbesondere 3 bis 6 Gew.- beträgt, wird die Plastifizierbarkeit des leichten Additivs verbessert und die Dichte des kompaktierten Additivs erhöht. Die Bindemittel können dem leichten Additiv zugemischt oder auf das leichte Granulat aufgesprüht werden, beispielsweise indem man den zur Walze geführten Pulverstrom mit Wasser oder wäßrigen Tensidlösungen be¬ sprüht. Wird als Bindemittel Wasser ausgewählt, so kann ein Wasserzusatz unterbleiben, wenn das beispielsweise durch Sprühtrocknung erhaltene Gra¬ nulat nicht vollständig getrocknet wurde, so daß ein Feuchtigkeitsrest, beispielsweise 6 bis 15 Gew.-% Wasser, in dem sprühgetrockneten Granulat erhalten blieb. Die Weiterverarbeitung derart schwachfeuchter Sprühgranu¬ late stellt eine bevorzugte Arbeitsweise dar.The granules according to the invention usually have a bulk density of 240 to 450 g / 1, usually one of 320 to 400 g / 1. If small amounts, for example 0.5 to 3% by weight, of surfactants, such as soaps, sulfonates, organic sulfates or alkylpolyglycosides, were added to the granules before the spray drying, the bulk density may be 50 to 150 g / l lower than without this addition. In a further and preferred embodiment, granules with a higher bulk density, in particular those of 500 to 900 g / 1, are claimed. The bulk density can be increased in a manner known per se by compacting the light granules, for which purpose in principle all techniques are suitable which are carried out under pressure and, if appropriate, with the addition of a small amount of liquid, for example by roller compaction, pelleting, extrusion or tableting. When compacting spray-dried additives, pressing by means of rollers, for example at a pressure between 100 and 200 bar, is preferred. Since the spray-dried granules have a certain plasticity under pressure, a flake-shaped product can be obtained in this way, which can then, if necessary, be comminuted to the desired particle size. The compacted products surprisingly retain their good dispersing and dissolving properties. The bulk density of such products is in particular between 650 and 800 g / l. Before or during compaction, liquid binders, preferably water and / or nonionic, in particular ethoxylated, nonionic surfactants, paste-like anionic surfactants and paraffin oil can be added to the granular additives. The addition of binder, the content of which, based on the compacted granulate, advantageously does not exceed 10% by weight, preferably 2 to 8% by weight and in particular 3 to 6% by weight, improves the plasticizability of the light additive and the density of the compacted additive increases. The binders can be mixed with the light additive or sprayed onto the light granulate, for example by spraying the powder stream fed to the roller with water or aqueous surfactant solutions. If water is selected as the binder, water can be omitted if the granules obtained, for example, by spray drying have not been completely dried, so that a residual moisture, for example 6 to 15% by weight of water, is retained in the spray-dried granules. The further processing of such slightly moist spray granules is a preferred method of operation.
Alternativ dazu kann man das Kompaktieren nach Zusatz entsprechender Flüssigkeitsmengen auch in einer Schneckenpresse bzw. in einer Granulier¬ vorrichtung durchführen. Ein anschließendes Nachtrocknen der kompaktierten Additive ist im allge¬ meinen nicht erforderlich und insbesondere auch nicht bevorzugt. Der Wirkstoffgehalt der nicht getrockneten Kompaktate verringert sich gering¬ fügig entsprechend der zugesetzten Flüssigkeitsmenge. Auch die kompak¬ tierten Granulate sind gut rieselfähig und übertreffen in ihrer Lagerfä¬ higkeit unter ungünstigen Bedingungen, beispielsweise in feuchter Atmo¬ sphäre, auch die sprühgetrockneten Produkte. As an alternative to this, the compacting can also be carried out in a screw press or in a granulating device after the addition of appropriate amounts of liquid. Subsequent post-drying of the compacted additives is generally not necessary and, in particular, is also not preferred. The active ingredient content of the non-dried compacts slightly decreases according to the amount of liquid added. The compacted granules are also free-flowing and their storage stability under unfavorable conditions, for example in a moist atmosphere, also exceeds the spray-dried products.
B e s p e l eB e s p e l e
Beispiel 1 :Example 1 :
Ein granuläres Additiv der Zusammensetzung (in Gew.-%)A granular additive of the composition (in% by weight)
60,0 % Acrylsäure-Maleinsäure-Copolymer (relative Molekülmasse60.0% acrylic acid-maleic acid copolymer (molecular weight
70000) in Form des Na-Salzes, 16,0 % Zeolith NaA, sprühgetrocknet (20 Gew.-% gebundenes Wasser), 10,6 % Natriumsulfat (wasserfrei),70000) in the form of the Na salt, 16.0% zeolite NaA, spray-dried (20% by weight bound water), 10.6% sodium sulfate (anhydrous),
8,0 % Natriumcarbonat (wasserfrei),8.0% sodium carbonate (anhydrous),
5,4 % Wasser wurde wie folgt hergestellt:5.4% water was produced as follows:
Ein auf 77 °C erwärmter Slurry, der die vorgenannten Feststoffe und 47,0 Gew.-% Wasser enthielt und eine Viskosität von 2500 mPa-s (60 °C; Kegelstumpfviskosimeter der Firma Brabender, Duisburg, Bundesrepublik Deutschland) aufwies, wurde mit einem Druck von 40 bar über Düsen in einem Trockenturm versprüht. Das im Gegenstrom geführte Trockengas wies eine Temperatur von 210 °C im Ringkanal und 120 °C im Bereich des Turmaustritts auf. Das Sprühprodukt war hervorragend rieselfähig und wies ein Schüttge¬ wicht von 320 g/1 auf. Durch Siebanalyse wurde die folgende Kornverteilung ermittelt (> größer als, < kleiner als)A slurry heated to 77 ° C, which contained the aforementioned solids and 47.0 wt .-% water and had a viscosity of 2500 mPa-s (60 ° C; truncated cone viscometer from Brabender, Duisburg, Federal Republic of Germany), was with a Pressure of 40 bar sprayed through nozzles in a drying tower. The counter-current dry gas had a temperature of 210 ° 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 320 g / l. The following particle size distribution was determined by sieve analysis (> greater than, <less than)
mm > 1.6 >0.8 >0.4 >0.2 >0.1 <Q.l Gew.-% 2 19 43 26 8 2mm> 1.6> 0.8> 0.4> 0.2> 0.1 <Q.l% by weight 2 19 43 26 8 2
Der Staubanteil (< 0,05 mm) lag unter 0,02 Gew.-%. Das Produkt erwies sich als gut lagerbeständig und in kaltem Wasser schnell und vollständig re- dispergierbar. Für die Weiterverwendung wurden die Anteile mit einer Korngröße über 1,6 mm und unter 0,1 mm durch Absieben abgetrennt.The dust content (<0.05 mm) was less than 0.02% by weight. The product proved to be stable in storage and quickly and completely redispersible in cold water. For further use, the parts with a grain size of more than 1.6 mm and less than 0.1 mm were separated off by sieving.
Beispiel 2:Example 2:
Wie in Beispiel 1 beschrieben, wurde ein rieselfähiges, lagerbeständiges Granulat folgender Zusammensetzung durch Sprühtrocknung hergestellt: 50,0 Gew.-% Na-Salz des Acrylsäure-Maleinsäure-Copolymers, 20,0 Gew.-% Zeolith NaA, sprühgetrocknet, 10,0 Gew.-% Natriumsulfat (wasserfrei), 9,0 Gew.-% Natriumcarbonat (wasserfrei), 11,0 Gew.-% Wasser.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, 20.0% by weight zeolite NaA, spray-dried, 10.0% by weight sodium sulfate (anhydrous), 9.0% by weight sodium carbonate ( anhydrous), 11.0% by weight water.
Produktionsbedingungen: Wassergehalt des Slurries 40,1 Gew.-%, Slurry- Temperatur 64 °C, Viskosität 2800 mPa*s (80 °C; Kegelstumpf-Viskosimeter der Firma Brabender, Duisburg, Bundesrepublik Deutschland), Sprühdruck 40 bar, Trockengastemperatur Eingang 220 °C, Ausgang 110 °C. Das Schütt¬ gewicht betrug 340 g/1. Siebanalyse:Production conditions: water content of the slurry 40.1% by weight, slurry temperature 64 ° C, viscosity 2800 mPa * s (80 ° C; truncated cone viscometer from Brabender, Duisburg, Federal Republic of Germany), spray pressure 40 bar, dry gas temperature inlet 220 ° C, outlet 110 ° C. The bulk density was 340 g / 1. Sieve analysis:
mm > 1.6 > 0.8 > 0.4 > 0.2 > 0.1 < 0.1mm> 1.6> 0.8> 0.4> 0.2> 0.1 <0.1
Gew.-% 1 14 46 27 9 3% By weight 1 14 46 27 9 3
Der Staubanteil lag unter 0,02 Gew.-%. Das Sprühprodukt zeigte eine gleich gute Rieselfähigkeit wie das Produkt gemäß Beispiel 1.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.
In analoger Weise wurden folgende Granulate hergestellt, wobei ein Copoly er entsprechend Beispiel 1 eingesetzt wurde.The following granules were prepared in an analogous manner, a copoly as in Example 1 being used.
Die Abkürzung APG steht für ein Alkylpolyglucosid, abgeleitet von linearen und mit einem mittleren Oligomerisierungsgrad des Glu- coserestes von 1,4. Das mit diesem Zusatz hergestellte Produkt zeichnet sich durch einen überdurchschnittlich hohen Weißgrad und ein vergleichs¬ weise niedriges Schüttgewicht aus. Das Produkt gemäß Beispiel 3 erfordert wegen seiner etwas erschwerten Trockenbarkeit einen etwas geringeren Pro¬ duktdurchsatz pro Zeiteinheit im Trockenturm. Alle Granulate waren gut rieselfähig und lagerbeständig und erwiesen sich beim Einbringen in kaltes Leitungswasser als vollständig und schnell redispergierbar.The abbreviation APG stands for an alkyl polyglucoside, derived from linear ones and with an average degree of oligomerization of the glucose residue of 1.4. The product made with this addition draws is characterized by an above-average degree of whiteness and a comparatively low bulk density. The product according to Example 3 requires a somewhat lower product throughput per unit of time in the drying tower because of its somewhat difficult drying properties. All granules were free-flowing and stable in storage and proved to be completely and quickly redispersible when introduced into cold tap water.
VeroleichsversucheAttempts to compare
Wie im vorstehenden Beispiel 1 beschrieben, wurden Sprühprodukte der fol¬ genden Zusammensetzung hergestellt (in Gew.-%):As described in Example 1 above, spray products of the following composition were produced (in% by weight):
A) 50,0 % Na-Salz des Acrylsäure-Maleinsäure-Copoly ers, 45,3 % Natriumcarbonat (wasserfrei),A) 50.0% Na salt of the acrylic acid-maleic acid copolymer, 45.3% sodium carbonate (anhydrous),
4,7 % Wasser.4.7% water.
B) 30,0 % Na-Salze des Copolymers, 54,8 % Natriumcarbonat (wasserfrei),B) 30.0% Na salts of the copolymer, 54.8% sodium carbonate (anhydrous),
5,0 % Natriumsulfat (wasserfrei), 10,2 % Wasser (Wasserbindung 1,07 Mol pro Mol Natriumcarbonat)5.0% sodium sulfate (anhydrous), 10.2% water (water binding 1.07 mol per mol sodium carbonate)
In Versuch A wurden die gleichen SprUhbedingungen angewandt wie im Bei¬ spiel 1 beschrieben, im Versuch B lag die Turmaustritt-Temperatur der Trockengase bei 90 °C. Beide Sprühprodukte bestanden aus klebrigen, be¬ reits unter leichtem Druck verformbaren Körnern. Das Rieselverhalten war unbefriedigend und bei dem Versuch, die Produkte zusammen mit weiteren Reiπigungs ittelbestandteilen zu stabilen Granulaten weiterzuverarbeiten, traten Störungen infolge Anklebung an den Mischorgan und der Innenwand des Granuliermischers auf.In experiment A the same spraying 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 which could already be deformed under slight pressure. The flow behavior was unsatisfactory and when trying to process the products together with other cleaning constituents into stable granules, problems occurred due to sticking to the mixing element and the inner wall of the granulating mixer.
Beispiele 7 und 8:Examples 7 and 8:
Zwecks Erhöhung des Schüttgewichtes wurden die Granulate gemäß Beispiel 1 •und 2 einem Walzenko paktierer zugeführt. Der Walzendruck betrug 150 bar. Das wasserärmere Granulat wurde vor dem Verpressen mit 4 Gew.-% Wasser bedüst, während das wasserreichere Produkt gemäß Beispiel 2 unmittelbar kompaktiert wurde. Das Preßgut wurde kontinuierlich in einer Hammerkorbmühle zerkleinert. Granulate mit einer Korngröße über 1,6 mm und weniger als 0,2 mm wurden abgesiebt. Die abgesiebten Fein- und Grobanteile wurden dem zu kompaktierenden Pulverstrom wieder zugeführt. Es resul¬ tierten hartkörnige, gut schüttfähige, abriebstabile Spl ttergranulate mit den folgenden Pulverspezifikationen.In order to increase the bulk density, the granules according to Example 1 • and 2 were fed to a roller compactor. The roller pressure was 150 bar. The lower-water granules were sprayed with 4% by weight of water before the pressing, while the more water-rich product was compacted according to Example 2. The pressed material was continuously in one Hammer basket grinder crushed. Granules with a grain size greater than 1.6 mm and less than 0.2 mm were sieved. The screened fine and coarse fractions were fed back into the powder stream to be compacted. The result was hard-grained, easily pourable, abrasion-resistant splinter granules with the following powder specifications.

Claims

Patentansprüche Claims
1. Granuläres Additiv für Wasch- und Reinigungsmittel, enthaltend1. Containing granular additive for detergents and cleaning agents
40 bis 75 Gew.-% an Natriumsalzen mindestens einer homopolymeren bzw. copolymeren (Meth-)Acrylsäure,40 to 75% by weight of sodium salts of at least one homopolymeric or copolymeric (meth) acrylic acid,
1 bis 35 Gew.-% an synthetischem, feinkristallinem, gebundenes Wasser enthaltenden Zeolith,1 to 35% by weight of synthetic, finely crystalline, zeolite containing bound water,
2 bis 20 Gew.-% Natriumsulfat (wasserfrei gerechnet) und 1 bis 15 Gew.-% Wasser.2 to 20% by weight sodium sulfate (calculated as anhydrous) and 1 to 15% by weight water.
2. Additiv nach Anspruch 1, gekennzeichnet durch einen Gehalt von2. Additive according to claim 1, characterized by a content of
45 bis 65 Gew.-% an homopolymeren oder copolymeren (Meth-)Acrylaten,45 to 65% by weight of homopolymeric or copolymeric (meth) acrylates,
8 bis 30 Gew.-% wasserhaltigen Zeolith,8 to 30% by weight of water-containing zeolite,
4 bis 15 Gew.-% Natriumsulfat (wasserfrei gerechnet),4 to 15% by weight sodium sulfate (calculated as anhydrous),
3 bis 15 Gew.-% Natriumcarbonat (wasserfrei gerechnet) und 3 bis 11 Gew.-% Wasser.3 to 15% by weight sodium carbonate (calculated as anhydrous) and 3 to 11% by weight water.
3. Additiv nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß mindestens 75 Gew.-%, vorzugsweise mindestens 85 Gew.-% der Granulate eine Größe von 0,2 bis 1,6 mm aufweisen, wobei der Anteil der Granulate mit einer Korngröße zwischen 0,1 und 0,05 mm nicht mehr als 4 Gew.-% und der Anteil der Granulate mit einer Korngröße zwischen 1,6 und 2,4 mm nicht mehr als 10 Gew.-% beträgt, und das Schüttgewicht zwischen 320 und 400 g/1 liegt.3. Additive according to claim 1 or 2, characterized in that at least 75 wt .-%, preferably at least 85 wt .-% of the granules have a size of 0.2 to 1.6 mm, the proportion of the granules having a grain size between 0.1 and 0.05 mm not more than 4% by weight and the proportion of the granules with a grain size between 1.6 and 2.4 mm is not more than 10% by weight, and the bulk density between 320 and 400 g / 1.
4. Additiv nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß es 2 bis 8 Gew.-% an flüssigen Bindemitteln enthält und ein Schüttgewicht zwi¬ schen 650 und 800 g/1 aufweist.4. Additive according to claim 1 or 2, characterized in that it contains 2 to 8 wt .-% of liquid binders and has a bulk density between 650 and 800 g / 1.
5. Verfahren zur Herstellung eines granulären Additivs für Wasch- und Reinigungsmittel, wobei das Additiv5. A process for the preparation of a granular additive for detergents and cleaning agents, the additive
40 bis 75 Gew.-% an Natriumsalzen mindestens einer homopolymeren bzw. copolymeren (Meth-)Acrylsäure, 1 bis 35 Gew.-% an synthetischem, feinkristallinem, gebundenes Wasser enthaltenden Zeolith,40 to 75% by weight of sodium salts of at least one homopolymeric or copolymeric (meth) acrylic acid, 1 to 35% by weight of synthetic, finely crystalline, zeolite containing bound water,
2 bis 20 Gew.-% Natriumsulfat (wasserfrei gerechnet) und 1 bis 15 Gew.-% Wasser enthält, dadurch gekennzeichnet, daß es durch Sprühtrocknung hergestellt wird.Contains 2 to 20 wt .-% sodium sulfate (calculated anhydrous) and 1 to 15 wt .-% water, characterized in that it is produced by spray drying.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß das sprühge¬ trocknete Granulat unter Druck kompaktiert wird.6. The method according to claim 5, characterized in that the spray-dried granules are compacted under pressure.
7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß man das zur Ko paktierung bestimmte sprühgetrocknete Granulat mit Wasser befeuch¬ tet und/oder als sprühgetrocknetes Granulat mit erhöhtem Wassergehalt einsetzt. 7. The method according to claim 6, characterized in that the spray-dried granules intended for Ko compacting are moistened with water and / or used as spray-dried granules with increased water content.
EP92904218A 1991-02-11 1992-02-03 Granular additive for washing and cleaning agents Expired - Lifetime EP0571436B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4104085 1991-02-11
DE4104085A DE4104085A1 (en) 1991-02-11 1991-02-11 GRANULAR ADDITIVE FOR DETERGENT AND CLEANING AGENT
PCT/EP1992/000227 WO1992013937A1 (en) 1991-02-11 1992-02-03 Granular additive for washing and cleaning agents

Publications (2)

Publication Number Publication Date
EP0571436A1 true EP0571436A1 (en) 1993-12-01
EP0571436B1 EP0571436B1 (en) 1995-06-21

Family

ID=6424804

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92904218A Expired - Lifetime EP0571436B1 (en) 1991-02-11 1992-02-03 Granular additive for washing and cleaning agents

Country Status (5)

Country Link
EP (1) EP0571436B1 (en)
AT (1) ATE124081T1 (en)
DE (2) DE4104085A1 (en)
ES (1) ES2073291T3 (en)
WO (1) WO1992013937A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4404279A1 (en) * 1994-02-10 1995-08-17 Henkel Kgaa Tablet with builder substances
DE19651072A1 (en) * 1996-12-09 1998-06-10 Henkel Kgaa Additive for detergents or cleaning agents
EP1529834A1 (en) * 2003-11-10 2005-05-11 The Procter & Gamble Company Detergent particles
EP1529833A1 (en) * 2003-11-10 2005-05-11 The Procter & Gamble Company Detergent particles

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3604223A1 (en) * 1985-02-14 1986-08-14 Basf Ag, 67063 Ludwigshafen Additive for detergents and cleaners
GB8626082D0 (en) * 1986-10-31 1986-12-03 Unilever Plc Detergent powders
GB8922179D0 (en) * 1989-10-02 1989-11-15 Rohm & Haas Polymer-containing granulates

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9213937A1 *

Also Published As

Publication number Publication date
ES2073291T3 (en) 1995-08-01
EP0571436B1 (en) 1995-06-21
WO1992013937A1 (en) 1992-08-20
DE59202625D1 (en) 1995-07-27
DE4104085A1 (en) 1992-08-13
ATE124081T1 (en) 1995-07-15

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