EP0716682A1 - Builder for washing or cleaning products - Google Patents

Builder for washing or cleaning products

Info

Publication number
EP0716682A1
EP0716682A1 EP94925465A EP94925465A EP0716682A1 EP 0716682 A1 EP0716682 A1 EP 0716682A1 EP 94925465 A EP94925465 A EP 94925465A EP 94925465 A EP94925465 A EP 94925465A EP 0716682 A1 EP0716682 A1 EP 0716682A1
Authority
EP
European Patent Office
Prior art keywords
weight
roller
crystalline layered
mixture
crystalline
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
EP94925465A
Other languages
German (de)
French (fr)
Other versions
EP0716682B1 (en
Inventor
Volker Bauer
Wolfgang Seiter
Jochen Jacobs
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
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Filing date
Publication date
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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
    • 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
    • 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
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
    • 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
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O

Definitions

  • the invention relates to a builder component with a very high bulk density and to detergents or cleaning agents which contain this component.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and fr-sodium disilicate a2Si2 ⁇ 5 * yH2 ⁇ are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.
  • ⁇ -sodium disilicate is commercially available under the name SKS 7 ( R )
  • fr-sodium disilicate is commercially available under the name SKS ⁇ ( R ) (commercial products from Hoechst AG, Federal Republic of Germany).
  • These powders generally have a bulk density of less than 600 g / l and have a high proportion of fine particles, usually more than 30% by weight, with a particle size of less than 0.1 mm.
  • the crystalline layered silicates are used in the form of a granular builders component which contains at least 10% by weight of crystalline layered silicates and 5 to 90% by weight in water in the form of ions of organic acids and / or inorganic or organic salts present, the material used, however, should not exceed an average size of 300 ⁇ m, and optionally further binders, surfactants and other conventional ingredients of detergents or cleaning agents contain.
  • a preferred way of producing this builder component is roller compaction, with a pressing pressure of 10 to 50 kN / cm roller length and preferably around 25 kN / cm roller length being used.
  • Such builders components still have high pH values in 1% aqueous solution; however, since these components have a higher dissolution rate than the powder, the risk of local deposits on textiles and thus damage to textile fibers is reduced.
  • Roll compacting of detergents or cleaning agents or individual components of detergents or cleaning agents is a state of the art. It is already known from European patent application EP-A-0 253 323 that builders such as zeolite and / or phosphate can be converted into granules with a high bulk density and very good application properties by roller compaction. The conditions under which roller compaction is usually carried out are described in detail in this prior art document. It is stated that the pressing pressure in the nip and the dwell time of the material in the area of the pressing pressure are to be set in such a way that a well-formed, high-density band is produced.
  • roller compaction is usually carried out at temperatures which are not additionally increased externally, but at ambient temperature.
  • the object of the invention was to further develop the method of roller compaction of builders components which contain crystalline layered silicates in such a way that a further improvement in the dissolving behavior of crystalline layered silicates or of builders components which contain crystalline layered silicates is achieved.
  • the invention accordingly relates to a process for the preparation of a builder component which contains at least 10% by weight of crystalline phyllosilicates of the formula aMSi x ⁇ 2 ⁇ + ⁇ * yH2 ⁇ , where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, by roller compacting at compression pressures of up to 50 kN / cm roller length, the crystalline sheet silicates and, if appropriate, other usual ingredients of washing or cleaning agents being compacted at roller temperatures between 35 and 120 ° C.
  • the invention encompasses both a method for roller compacting solely crystalline layered silicates, that is to say without additives, and also mixtures of crystalline layered silicates and customary further ingredients of washing or cleaning agents. If mixtures of crystalline layered silicates and conventional ingredients of washing or cleaning agents are used, it is preferred that the content of the mixture of crystalline layered silicates is 50 to 99.5% by weight and in particular 60 to 90% by weight. Disilicates, and in particular ⁇ -sodium disilicate and / or fr-sodium disilicate, are used as particularly preferred crystalline layered silicates.
  • Preferred mixtures which are used in roller compaction are those which contain crystalline phyllosilicates and salts of inorganic and / or organic acids, in particular honor-based acids, the content of the mixture of these salts preferably being 0.5 to 50 % By weight and in particular 10 to 40% by weight.
  • Preferred salts of inorganic polybasic acids are sulfates and carbonates, sodium sulfate being particularly preferred, while citrates with particular preference for sodium citrate are preferred on salts of organic polybasic acids.
  • Preferred organic acids are adipic acid, succinic acid, citric acid and glutaric acid, citrate and one or more organic acids also being able to be used in particularly preferred embodiments.
  • the roller compacting is carried out in a mixture which consists of 70 to 90% by weight of ⁇ -sodium disilicate and / or fr-sodium disilicate and 10 to 30% by weight of sodium sulfate and / or sodium citrate.
  • the mixtures to be compacted can contain, in addition to or instead of these salts of inorganic and / or organic acids, other conventional ingredients of detergents or cleaning agents. Which ingredients may be suitable for this purpose can also be found in international patent application WO-A-92/18594.
  • mixtures which contain crystalline layered silicates and conventional builders such as phosphates and / or zeolites. It is particularly preferred that the zeolite content of the mixture is preferably 0.5 to 50% by weight and in particular 1 to 20% by weight.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality.
  • zeolite NaX and zeolite P and mixtures of NaA, NaX and P are also suitable, for example.
  • the zeolite is preferably used as a spray-dried powder with an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter counter) and preferably contains 18 to 22% by weight and in particular 20 to 22% by weight of bound water.
  • Mixtures which contain 0 to 20% by weight and preferably 0 to 10% by weight of further customary ingredients of detergents or cleaning agents can also be used in roller compacting.
  • the substance mixtures are preferably mixed with one another in powder form.
  • liquid constituents are also incorporated into the mixture of substances, it is Roll compaction not required.
  • components of detergents or cleaning agents which are in liquid form at the processing temperature are not used;
  • components of detergents or cleaning agents which are also in liquid form at room temperature are not used in amounts above 5% by weight, based on the mixture, and advantageously not at all.
  • the mixtures of substances can be produced in conventional mixers or granulators. Pre-compaction of the powder is also possible.
  • the roller pressing itself can, however, take place without or with a pre-compression of the premixed powdery material.
  • the pair of rollers can be arranged in any spatial direction, in particular thus vertically or horizontally to one another.
  • the mixture to be compacted or the sole powder of crystalline layered silicate is then fed to the roll gap either by gravity filling or by means of a suitable device, for example by means of a stuffing screw.
  • the material to be compacted is then passed under pressure through the gap of a pair of two rollers running in opposite directions at approximately the same circumferential speed and compacted to form a plate-like or band-shaped material to be pressed, which is also referred to as a sling band.
  • Preferred press pressures are between 7 and 30 kN / cm roll length and in particular press presses between 10 and 25 kN / cm roll length.
  • roller compaction of crystalline layered silicates or of solid mixtures containing crystalline layered silicates can not only be carried out without problems at elevated temperatures, but that this increased temperature also improves the dissolution behavior of the crystalline ones further Layered silicates or the builders components, which contain crystalline layered silicates, is achieved.
  • Roll temperatures between 40 and 100 ° C and in particular between 45 and 90 ° C are particularly preferred.
  • a roller compacting has been found to be particularly advantageous, which is carried out at roller temperatures between 50 and 70 ° C. and at pressing pressures between 12 and 20 kN / cm roller length.
  • the shoulder strap is then subjected to a comminution process.
  • This comminution or grinding can take place, for example, in a mill.
  • the comminuted material is then expediently fed to a screening process, coarse material being separated off and returned to the comminution device, while material which is too fine is added again to the batch of the powdery mixture or the powdery layered silicate and fed again to the compacting in the roll gap becomes.
  • the sliver belt is preferably made by conventional grinding into granules with a particle size range from 0.05 mm to about 2 mm, preferably with a particle size range consisting of at least 70% by weight of granules with a particle diameter between 0.1 and 1.6 mm there is set, while fine grain fractions with granule diameters below 0.05 mm are returned to the compacting and coarse grain fractions with granule diameters above 2 mm are returned to the grinding.
  • a granular builder component is obtained which has a bulk density between 800 and 1100 g / 1.
  • the granular builder components obtained which in this case preferably consist of 100% by weight of crystalline layered silicates, are selected in a subsequent step with further ingredients of washing or cleaning agents, preferably with impregnating agents from the group of ethoxylated nonionic surfactants, mixtures of non-ionic and anionic surfactants, paste-like aqueous nonionic and / or anionic surfactants, the water possibly being subsequently dried off, and silicone oils and paraffin oils, in particular with nonionic surfactants, acted upon.
  • the builder components can then additionally be powdered off with powdery solids, in particular with powdery crystalline layered silicates.
  • the invention relates to a washing or cleaning agent which contains the builders components according to the invention.
  • these agents preferably contain the Gerüststoffko components according to the invention in amounts of 10 to 70 wt .-% and in particular in amounts of 20 to 60 wt .-%.
  • the washing or cleaning agents contain further conventional inorganic and / or organic builders, contents of 25 to 50% by weight of the builders components according to the invention are particularly advantageous.
  • the washing or cleaning agents can contain all the usual ingredients such as anionic, nonionic, amphoteric, cationic and / or zwitterionic surfactants, other builders such as zeolite and / or phosphates, layered silicates such as bentonites, polycarboxylates such as citrates etc., polymeric polycarboxylates such as Contain salts of homo- or copolymers of acrylic acid, bleaching agents and bleach activators, graying inhibitors such as cellulose ethers or polyvinylpyrrolidone, optical brighteners, dyes and fragrances, and enzymes and enzyme stabilizers. Foam inhibitors can also be included.
  • the agents can consist of a basic granulate or of a multicomponent mixture, whereby multicomponent mixtures can be advantageous.
  • enzyme granules and, for example, bleach activator granules, but also foam inhibitor granules or individual components such as sodium carbonate, sodium silicate or polycarboxylate, are subsequently mixed in.
  • the individual components can be produced by spray drying, granulation, extrusion or other conventional techniques.
  • the agents have a bulk density above 650 g / 1, preferably above 700 g / 1.
  • detergents or cleaning agents with bulk densities above 800 g / l can also be produced without these agents tending to separate.
  • These agents are also suitable for concentrates with high surfactant contents.
  • a high anionic surfactant content can be obtained by adding a highly concentrated anionic surfactant compound obtained, for example, by spray drying, spray neutralization or by granulation and simultaneous drying in a fluidized bed, and a high nonionic surfactant content by admixing the builder components with high nonionic surfactant components can be achieved.
  • Detergents or cleaning agents with 15 to 40% by weight, in particular with 18 or 20 to 35% by weight, anionic and nonionic surfactants are preferred.
  • the invention Roll-compacted granules, preferably coated with nonionic surfactants, are added to extruded granules which may contain highly concentrated anionic surfactant compounds and are preferably non-surfactant-ar to, in particular, non-surfactant-free.
  • Crystalline layered silicates of the type SKS ⁇ ( R ) (HT sodium disilicate, commercial product from Hoechst AG, Germany) or the mixtures of SKS 6 ( R ) and the inorganic or organic salts of polybasic acids given below were mixed on a Roll press of the type WR 50 N / 75 (Alexanderwerk AG, Germany) pressed at the temperatures given below to form shoulders of approx. 1 mm thickness. After comminution into granules with an average particle size range of 0.1 to 1.6 mm, products with the bulk densities specified below were obtained. The dissolving speeds given in the table were determined for the sieve fraction 0.6 to 0.8 m according to the following test:
  • SKS 600 100 100 80 80 80 80 in% by weight

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The object of the invention is to obtain a roller compacted builder with an improved solubility that contains at least 10 % by weight crystalline stratified silicates having the formula NaMSixO2x+1.yH2O, in which M stands for sodium or hydrogen, x equals 1.9 to 4 and y 0 to 20. For that purpose, the crystalline stratified silicates and if required other usual ingredients of washing or cleaning products are roller compacted at roller temperatures from 35 to 120 DEG C.

Description

"Gerüststoff o ponente für Wasch- oder Reinigungsmittel" "Builders component for detergents or cleaning agents"
Die Erfindung betrifft eine Gerüststoffkomponente mit sehr hohem Schütt¬ gewicht sowie Wasch- oder Reinigungsmittel, welche diese Komponente ent¬ halten.The invention relates to a builder component with a very high bulk density and to detergents or cleaning agents which contain this component.
Kristalline schichtförmige Natriumsilikate der Formel Na Sixθ2χ+ yH2θ, wobei Natrium oder Wasserstoff bedeutet, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte für x 2, 3 oder 4 sind, haben sich als geeignete Substitute oder Teilsubstitute für die etablier¬ ten Gerüststoffe Phosphate und Zeolithe erwiesen. Derartige kristalline Schichtsilikate werden beispielsweise in der europäischen Patentanmeldung EP-A-0 164 514 beschrieben. Bevorzugte kristalline Schichtsilikate sind solche, in denen M für Natrium steht und x die Werte 2 oder 3 annimmt. Insbesondere sind sowohl ß- als auch fr-Natriumdisilikate a2Si2θ5*yH2θ bevorzugt, wobei ß-Natriumdisilikat beispielsweise nach dem Verfahren er¬ halten werden kann, das in der internationalen Patentanmeldung WO-A-91/ 08171 beschrieben ist. ß-Natriumdisilikat ist unter der Bezeichnung SKS 7(R), fr-Natriumdis likat ist unter der Bezeichnung SKS β(R) im Handel er¬ hältlich (Handelsprodukte der Hoechst AG, Bundesrepublik Deutschland). Diese Pulver weisen im allgemeinen ein Schüttgewicht unter 600 g/1 auf und besitzen hohe Feinkornanteile, üblicherweise mehr als 30 Gew.-%, mit einer Teilchengröße unterhalb 0,1 mm. Da kristalline Schichtsilikate gemäß der Offenbarung der internationalen Patentanmeldung W0-A-92/18594 bei der Sprühtrocknung Wasch- oder Reinigungsmittel-haltiger Slurries Verluste in ihrer Waschwirkung, hervorgerufen durch die Zerstörung ihrer physika¬ lischen Struktur, erleiden, sollten sie vorzugsweise über andere Verfah¬ rensmethoden in Wasch- oder Reinigungsmittel eingearbeitet werden. Auf¬ grund ihres hohen Feinkornanteils und damit ihrer staubigen Struktur sind diese Pulver jedoch auch nicht geeignet, als Zumischkomponente zu anderen granulären Bestandteilen von Wasch- oder Reinigur^smitteln zu dienen. Da zudem kristalline Schichtsilikate wie kristallin Disilikate eine gerin¬ gere Lösegeschwindigkeit in Wasser aufweisen als amorphe Silikate, kann es durch lokale Ablagerungen auf den Textilien zu einem Anstieg des pH-Werts auf Werte oberhalb von 12 kommen, wodurch Beschädigungen der Textilfasern entstehen können. Die internationale Patentanmeldung W0-A-92/18594 beschreibt, wie diese Nachteile vermieden werden können: Die kristallinen Schichtsilikate werden in Form einer granulären Gerüststoffko ponente eingesetzt, die mindestens 10 Gew.-% kristalline Schichtsilikate, 5 bis 90 Gew.-% in Wasser in Form von Ionen vorliegender organischer Säuren und/oder anorganischer oder or¬ ganischer Salze, wobei das eingesetzte Material allerdings eine Größe von im Durchschnitt 300 μm nicht überschreiten soll, sowie gegebenenfalls wei¬ tere Bindemittel, Tenside und weitere übliche Inhaltsstoffe von Wasch¬ oder Reinigungsmitteln enthalten. Eine bevorzugte Art der Herstellung die¬ ser Gerüststoffkomponente ist die Walzenkompaktierung, wobei ein Preßdruck von 10 bis 50 kN/cm Walzenlänge und vorzugsweise um 25 kN/cm Walzenlänge aufgewendet wird. Derartige Gerüststoffkomponenten weisen zwar in l%iger wäßriger Lösung immer noch hohe pH-Werte auf; da diese Komponenten jedoch gegenüber dem Pulver eine höhere Lösegeschwindigkeit besitzen, wird das Risiko der lokalen Ablagerungen auf Textilien und damit der Beschädigungen von Textilfasern verringert.Crystalline layered sodium silicates of the formula Na Si x θ2χ + yH2θ, where sodium or hydrogen means, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 have been proven as suitable substitutes or partial substitutes for the established builders phosphates and zeolites. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and fr-sodium disilicate a2Si2θ5 * yH2θ are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171. β-sodium disilicate is commercially available under the name SKS 7 ( R ), fr-sodium disilicate is commercially available under the name SKS β ( R ) (commercial products from Hoechst AG, Federal Republic of Germany). These powders generally have a bulk density of less than 600 g / l and have a high proportion of fine particles, usually more than 30% by weight, with a particle size of less than 0.1 mm. Since crystalline layered silicates, according to the disclosure of international patent application W0-A-92/18594, suffer from losses in their washing action caused by the destruction of their physical structure in the spray drying of detergent-containing or detergent-containing slurries, they should preferably be subjected to other methods can be incorporated into detergents or cleaning agents. However, owing to their high proportion of fine grains and thus their dusty structure, these powders are also not suitable for serving as an admixture component with other granular constituents of detergents or cleaning agents. Since, in addition, crystalline layered silicates such as crystalline disilicates have a lower dissolution rate in water than amorphous silicates, local deposits on the textiles can lead to an increase in the pH to values above 12, which can damage the textile fibers. International patent application WO-A-92/18594 describes how these disadvantages can be avoided: the crystalline layered silicates are used in the form of a granular builders component which contains at least 10% by weight of crystalline layered silicates and 5 to 90% by weight in water in the form of ions of organic acids and / or inorganic or organic salts present, the material used, however, should not exceed an average size of 300 μm, and optionally further binders, surfactants and other conventional ingredients of detergents or cleaning agents contain. A preferred way of producing this builder component is roller compaction, with a pressing pressure of 10 to 50 kN / cm roller length and preferably around 25 kN / cm roller length being used. Such builders components still have high pH values in 1% aqueous solution; however, since these components have a higher dissolution rate than the powder, the risk of local deposits on textiles and thus damage to textile fibers is reduced.
Die Walzenkompaktierung von Wasch- oder Reinigungsmitteln oder einzelner Komponenten von Wasch- oder Reinigungsmitteln ist gesicherter Stand des technischen Wissens. Bereits aus der europäischen Patentanmeldung EP-A-0 253 323 ist bekannt, daß Gerüststoffe wie Zeolith und/oder Phosphat durch Walzenkompaktierung in Granulate mit hohem Schüttgewicht und sehr guten anwendungstechnischen Eigenschaften überführt werden können. In diesem druckschriftlichen Stand der Technik werden ausführlich die Bedingungen geschildert, unter denen eine Walzenkompaktierung üblicherweise durchge¬ führt wird. Dabei wird ausgeführt, daß der Preßdruck im Walzenspalt und die Verweildauer des Materials in dem Bereich des Preßdrucks so einzustel¬ len sind, daß ein gut ausgebildetes Schülpenband mit hoher Dichte erzeugt wird. Der hohe Verdichtungsgrad ist dabei nicht nur im Hinblick auf mo¬ derne Wasch- oder Reinigungsmittel mit hohem Schüttgewicht, sondern auch hinsichtlich einer erhöhten Abriebstabilität der Granulate erwünscht. Da¬ bei muß allerdings beachtet werden, daß zu hohe Preßdrucke die Verfahrens¬ sicherheit beeinträchtigen, da bei ihrem Einsatz das Material auf den Wal¬ zen plastifiziert wird und zu Anklebungen führen kann. Dieser unerwünschte Effekt tritt dann auf, wenn eine Erhöhung des Preßdrucks keine weitere Verdichtung des Materials mehr bewirkt und die jetzt zusätzlich eingetra- gene Preßkraft überwiegend die Erwärmung und Plastifizierung des MaterialsRoll compacting of detergents or cleaning agents or individual components of detergents or cleaning agents is a state of the art. It is already known from European patent application EP-A-0 253 323 that builders such as zeolite and / or phosphate can be converted into granules with a high bulk density and very good application properties by roller compaction. The conditions under which roller compaction is usually carried out are described in detail in this prior art document. It is stated that the pressing pressure in the nip and the dwell time of the material in the area of the pressing pressure are to be set in such a way that a well-formed, high-density band is produced. The high degree of compaction is desired not only with regard to modern washing or cleaning agents with a high bulk density, but also with regard to increased abrasion stability of the granules. It must be noted, however, that excessively high compression pressures impair the process reliability, since when they are used the material is plasticized on the rollers and can lead to sticking. This undesirable effect occurs when an increase in the compression pressure no longer causes further compression of the material and the additional gene pressing force mainly the heating and plasticization of the material
- beispielsweise durch partielles Aufschmelzen wasserhaltiger Bestandteile- For example, by partially melting water-containing components
- verursacht. Dies ist auch der Grund dafür, daß Walzenkompaktierungen üblicherweise bei nicht zusätzlich extern erhöhten Temperaturen, sondern bei Umgebungstemperatur durchgeführt werden.- caused. This is also the reason why roller compaction is usually carried out at temperatures which are not additionally increased externally, but at ambient temperature.
Die Aufgabe der Erfindung bestand darin, das Verfahren der Walzenkompak¬ tierung von Gerüststoffkomponenten, welche kristalline Schichtsilikate enthalten, dahingehend weiterzuentwiekeln, daß eine weitere Verbesserung des Löseverhaltens von kristallinen Schichtsilikaten bzw. von Gerüststoff- komponenten, welche kristalline Schichts likate enthalten, erreicht wird.The object of the invention was to further develop the method of roller compaction of builders components which contain crystalline layered silicates in such a way that a further improvement in the dissolving behavior of crystalline layered silicates or of builders components which contain crystalline layered silicates is achieved.
Gegenstand der Erfindung ist dementsprechend ein Verfahren zur Herstellung einer Gerüststoffkomponente, welche mindestens 10 Gew.-% kristalline Schichtsilikate der Formel aMSixθ2χ+ι*yH2θ enthält, wobei M Natrium oder Wasserstoff bedeutet, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist, durch Walzenkompaktierung bei Preßdrucken bis 50 kN/cm Walzenlän¬ ge, wobei die kristallinen Schichtsilikate und gegebenenfalls weitere üb¬ liche Inhaltsstoffe von Wasch- oder Reinigungsmitteln bei Walzentempera¬ turen zwischen 35 und 120 °C kompaktiert werden.The invention accordingly relates to a process for the preparation of a builder component which contains at least 10% by weight of crystalline phyllosilicates of the formula aMSi x θ2χ + ι * yH2θ, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, by roller compacting at compression pressures of up to 50 kN / cm roller length, the crystalline sheet silicates and, if appropriate, other usual ingredients of washing or cleaning agents being compacted at roller temperatures between 35 and 120 ° C.
Die Erfindir umfaßt dabei sowohl ein Verfahren zur Walzenkompaktierung allein von kristallinen Schichtsilikaten, also ohne Zuschlagstoffe, als auch von Mischungen aus kristallinen Schichtsilikaten und üblichen wei¬ teren Inhaltsstoffen von Wasch- oder Reinigungsmitteln. Falls Mischungen aus kristallinen Schichtsilikaten und üblichen Inhaltsstoffen von Wasch¬ oder Reinigungsmitteln eingesetzt werden, so ist es bevorzugt, daß der Gehalt der Mischung an kristallinen Schichtsilikaten 50 bis 99,5 Gew.-% und insbesondere 60 bis 90 Gew.-% beträgt. Als besonders bevorzugte kri¬ stalline Schichts likate werden Disilikate und dabei vor allem ß-Natrium¬ disilikat und/oder fr-Natriumdisilikat eingesetzt.The invention encompasses both a method for roller compacting solely crystalline layered silicates, that is to say without additives, and also mixtures of crystalline layered silicates and customary further ingredients of washing or cleaning agents. If mixtures of crystalline layered silicates and conventional ingredients of washing or cleaning agents are used, it is preferred that the content of the mixture of crystalline layered silicates is 50 to 99.5% by weight and in particular 60 to 90% by weight. Disilicates, and in particular β-sodium disilicate and / or fr-sodium disilicate, are used as particularly preferred crystalline layered silicates.
Bevorzugte Mischungen, welche bei der Walzenkompaktierung eingesetzt wer¬ den, sind solche, die kristalline Schichtsilikate und Salze anorganischer und/oder organischer Säuren, insbesondere ehrbasiger Säuren, enthalten, wobei der Gehalt der Mischung an diesen Salzen vorzugsweise 0,5 bis 50 Gew.-% und insbesondere 10 bis 40 Gew.-% beträgt. Bevorzugte Salze anor¬ ganischer mehrbasiger Säuren sind Sulfate und Carbonate, wobei Natrium¬ sulfat insbesondere bevorzugt ist, während an Salzen organischer mehr¬ basiger Säuren Citrate mit besonderer Bevorzugung von Natriumeitrat be¬ vorzugt sind. Bevorzugte organische Säuren sind Adipinsäure, Bernstein¬ säure, Citronensäure und Glutarsäure, wobei in besonders bevorzugten Aus¬ führungsformen auch Citrat und ein oder mehrere organische Säuren einge¬ setzt werden können. In einer besonders bevorzugten Ausführungsform der Erfindung wird dabei die Walzenkompaktierung einer Mischung durchgeführt, die aus 70 bis 90 Gew.-% ß-Natriumdisilikat und/oder fr-Natriumdisilikat und aus 10 bis 30 Gew.-% Natriumsulfat und/oder Natriumeitrat besteht.Preferred mixtures which are used in roller compaction are those which contain crystalline phyllosilicates and salts of inorganic and / or organic acids, in particular honor-based acids, the content of the mixture of these salts preferably being 0.5 to 50 % By weight and in particular 10 to 40% by weight. Preferred salts of inorganic polybasic acids are sulfates and carbonates, sodium sulfate being particularly preferred, while citrates with particular preference for sodium citrate are preferred on salts of organic polybasic acids. Preferred organic acids are adipic acid, succinic acid, citric acid and glutaric acid, citrate and one or more organic acids also being able to be used in particularly preferred embodiments. In a particularly preferred embodiment of the invention, the roller compacting is carried out in a mixture which consists of 70 to 90% by weight of β-sodium disilicate and / or fr-sodium disilicate and 10 to 30% by weight of sodium sulfate and / or sodium citrate.
Die zu kompaktierenden Mischungen können jedoch zusätzlich oder anstelle dieser Salze anorganischer und/oder organischer Säuren andere übliche In¬ haltsstoffe von Wasch- oder Reinigungsmitteln enthalten. Welche Inhalts¬ stoffe dazu gegebenenfalls geeignet sind, kann auch der internationalen Patentanmeldung W0-A-92/18594 entnommen werden. In einer bevorzugten Aus¬ führungsform der Erfindung werden dabei Mischungen eingesetzt, die kri¬ stalline Schichtsilikate und herkömmliche Gerüststoffe wie Phosphate und/oder Zeolithe enthält. Dabei ist es insbesondere bevorzugt, daß der Gehalt der Mischung an Zeolith vorzugsweise 0,5 bis 50 Gew.-% und insbe¬ sondere 1 bis 20 Gew.-% beträgt. Der eingesetzte feinkristalline, synthe¬ tisches und gebundenes Wasser enthaltende Zeolith ist dabei vorzugsweise Zeolith NaA in Waschmittelqualität. Geeignet sind jedoch beispielsweise auch Zeolith NaX und Zeolith P sowie Mischungen aus NaA, NaX und P. Der Zeolith wird vorzugsweise als sprühgetrocknetes Pulver mit einer mittleren Teilchengröße von weniger als 10 μm (Volumenverteilung; Meßmethode: Coulter-Counter) eingesetzt und enthält vorzugsweise 18 bis 22 Gew.% und insbesondere 20 bis 22 Gew.-% an gebundenem Wasser.However, the mixtures to be compacted can contain, in addition to or instead of these salts of inorganic and / or organic acids, other conventional ingredients of detergents or cleaning agents. Which ingredients may be suitable for this purpose can also be found in international patent application WO-A-92/18594. In a preferred embodiment of the invention, mixtures are used which contain crystalline layered silicates and conventional builders such as phosphates and / or zeolites. It is particularly preferred that the zeolite content of the mixture is preferably 0.5 to 50% by weight and in particular 1 to 20% by weight. The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality. However, zeolite NaX and zeolite P and mixtures of NaA, NaX and P are also suitable, for example. The zeolite is preferably used as a spray-dried powder with an average particle size of less than 10 μm (volume distribution; measurement method: Coulter counter) and preferably contains 18 to 22% by weight and in particular 20 to 22% by weight of bound water.
Weiterhin können bei der Walzenkompaktierung Mischungen eingesetzt werden, welche 0 bis 20 Gew.-% und vorzugsweise 0 bis 10 Gew.-% weitere übliche Inhaltsstoffe von Wasch- oder Reinigungsmitteln enthalten. Bei der Her¬ stellung der Mischungen werden die Stoffgemische vorzugsweise in Pulver¬ form miteinander vermischt. Es ist zwar möglich, daß auch flüssige Be¬ standteile in das Stoffgemisch eingearbeitet werden, es ist jedoch zur Walzenkompaktierung nicht erforderlich. Im Gegenteil ist es sogar bevor¬ zugt, daß Bestandteile von Wasch- oder Reinigungsmitteln, die bei der Ver¬ arbeitungstemperatur in flüssiger Form vorliegen, nicht eingesetzt werden; insbesondere ist es bevorzugt, daß Bestandteile von Wasch- oder Reini¬ gungsmitteln, welche auch bei Raumtemperatur in flüssiger Form vorliegen, nicht in Mengen oberhalb 5 Gew.-%, bezogen auf die Mischung, und vorteil¬ hafterweise gar nicht eingesetzt werden. Die Stoffgemische können dabei in üblichen Mischern oder Granulatoren hergestellt werden. Dabei ist auch eine Vorverdichtung des Pulvers möglich.Mixtures which contain 0 to 20% by weight and preferably 0 to 10% by weight of further customary ingredients of detergents or cleaning agents can also be used in roller compacting. In the preparation of the mixtures, the substance mixtures are preferably mixed with one another in powder form. Although it is possible that liquid constituents are also incorporated into the mixture of substances, it is Roll compaction not required. On the contrary, it is even preferred that components of detergents or cleaning agents which are in liquid form at the processing temperature are not used; In particular, it is preferred that components of detergents or cleaning agents which are also in liquid form at room temperature are not used in amounts above 5% by weight, based on the mixture, and advantageously not at all. The mixtures of substances can be produced in conventional mixers or granulators. Pre-compaction of the powder is also possible.
Die Walzenverpressung selber kann aber ohne oder mit einer Vorverdichtung des vorgemischten pulverförmigen Gutes erfolgen. Das Walzenpaar kann dabei in jeder beliebigen Raumrichtung, insbesondere also vertikal oder horizon¬ tal zueinander angeordnet sein. Die zu kompaktierende Mischung oder das alleinige Pulver aus kristallinem Schichtsilikat wird dann entweder durch Schwerkraftfüllung oder mittels einer geeigneten Einrichtung, beispiels¬ weise mittels einer Stopfschnecke dem Walzenspalt zugeführt. Das zu kom- paktierende Gut wird dann unter Preßdruck durch den Spalt eines Paares zweier mit etwa gleicher Umfangsgeschwindigkeit gegensinnig laufender Wal¬ zen geführt und dabei zu einem plattenförmigen bzw. bandförmigen Preßgut, das auch als Schülpenband bezeichnet wird, verdichtet. Bevorzugte Pre߬ drucke liegen dabei zwischen 7 und 30 kN/cm Walzenlänge und insbesondere bei Preßdrucken zwischen 10 und 25 kN/cm Walzenlänge.The roller pressing itself can, however, take place without or with a pre-compression of the premixed powdery material. The pair of rollers can be arranged in any spatial direction, in particular thus vertically or horizontally to one another. The mixture to be compacted or the sole powder of crystalline layered silicate is then fed to the roll gap either by gravity filling or by means of a suitable device, for example by means of a stuffing screw. The material to be compacted is then passed under pressure through the gap of a pair of two rollers running in opposite directions at approximately the same circumferential speed and compacted to form a plate-like or band-shaped material to be pressed, which is also referred to as a sling band. Preferred press pressures are between 7 and 30 kN / cm roll length and in particular press presses between 10 and 25 kN / cm roll length.
Überraschenderweise wurde gefunden, daß die Walzenkompaktierung von kri¬ stallinen Schichtsilikaten oder von festen Stoffgemisehen, welche kristal¬ line Schichtsilikate enthalten, nicht nur problemlos bei erhöhten Tempera¬ turen durchgeführt werden kann, sondern daß durch diese erhöhte Temperatur auch eine weitere Verbesserung des Löseverhaltens der kristallinen Schichtsilikate bzw. der Gerüststoffkomponenten, welche kristalline Schichtsilikate enthalten, erreicht wird. Dabei sind Walzentemperaturen zwischen 40 und 100 °C und insbesondere zwischen 45 und 90 °C besonders bevorzugt. Als besonders vorteilhaft hat sich dabei eine Walzenkompaktie¬ rung erwiesen, die bei Walzentemperaturen zwischen 50 und 70 °C und bei Preßdrucken zwischen 12 und 20 kN/cm Walzenlänge durchgeführt wird. Das Schülpenband wird anschließend einem Zerkleinerungsverfahren unterwor¬ fen. Diese Zerkleinerung oder Mahlung kann dabei beispielsweise in einer Mühle erfolgen. Zweckmäßigerweise wird das zerkleinerte Material an¬ schließend einem Sichtungsprozeß zugeführt, wobei grobes Material abge¬ trennt und in die Zerkleinerungsvorrichtung zurückgeführt wird, während zu feines Material dem Ansatz der pulverför igen Mischung oder dem pulverför- migen Schichtsilikat wieder beigegeben und erneut der Kompaktierung im Walzenspalt zugeführt wird. Vorzugsweise wird dabei das Schülpenband durch übliche Mahlung in Granulate mit einem Kornspektrum von 0,05 mm bis etwa 2 mm, vorzugsweise mit einem Kornspektrum, das zu mindestens 70 Gew.-% aus Granulaten mit einem Teilchendurchmesser zwischen 0,1 und 1,6 mm besteht, eingestellt, während Feinkornanteile mit Granulatdurchmessern unterhalb 0,05 mm in die Kompaktierung zurückgeführt und Grobkornanteile mit Granu¬ latdurchmessern oberhalb 2 mm in die Mahlung zurückgeführt werden.Surprisingly, it was found that the roller compaction of crystalline layered silicates or of solid mixtures containing crystalline layered silicates can not only be carried out without problems at elevated temperatures, but that this increased temperature also improves the dissolution behavior of the crystalline ones further Layered silicates or the builders components, which contain crystalline layered silicates, is achieved. Roll temperatures between 40 and 100 ° C and in particular between 45 and 90 ° C are particularly preferred. A roller compacting has been found to be particularly advantageous, which is carried out at roller temperatures between 50 and 70 ° C. and at pressing pressures between 12 and 20 kN / cm roller length. The shoulder strap is then subjected to a comminution process. This comminution or grinding can take place, for example, in a mill. The comminuted material is then expediently fed to a screening process, coarse material being separated off and returned to the comminution device, while material which is too fine is added again to the batch of the powdery mixture or the powdery layered silicate and fed again to the compacting in the roll gap becomes. The sliver belt is preferably made by conventional grinding into granules with a particle size range from 0.05 mm to about 2 mm, preferably with a particle size range consisting of at least 70% by weight of granules with a particle diameter between 0.1 and 1.6 mm there is set, while fine grain fractions with granule diameters below 0.05 mm are returned to the compacting and coarse grain fractions with granule diameters above 2 mm are returned to the grinding.
In einer bevorzugten Ausführungform der Erfindung wird dabei eine gra¬ nuläre Gerüststoffkomponente erhalten, welche ein Schüttgewicht zwischen 800 und 1100 g/1 aufweist.In a preferred embodiment of the invention, a granular builder component is obtained which has a bulk density between 800 and 1100 g / 1.
In einer weiteren bevorzugten Ausführungsform der Erfindung werden die erhaltenen granulären Gerüststoffkomponenten, welche in diesem Fall vor¬ zugsweise aus 100 Gew.-% kristallinen Schichts likaten bestehen, in einem anschließenden Schritt mit weiteren Inhaltsstoffen von Wasch- oder Rei¬ nigungsmitteln, vorzugweise mit Imprägnierungsmitteln ausgewählt aus der Gruppe der ethoxylierten nichtionischen Tenside, Mischungen aus nicht¬ ionischen und anionischen Tensiden, pastenför igen wäßrigen nichtionischen und/oder anionischen Tensiden, wobei das Wasser gegebenenfalls nachträg¬ lich weggetrocknet wird, sowie der Silikonöle und Paraffinöle, insbeson¬ dere mit nichtionischen Tensiden, beaufschlagt. Im Anschluß an diese Imprägnierung können die Gerüststoffkomponenten dann zusätzlich mit pul¬ verförmigen Feststoffen, insbesondere mit pulverförmigen kristallinen Schichtsilikaten abgepudert werden.In a further preferred embodiment of the invention, the granular builder components obtained, which in this case preferably consist of 100% by weight of crystalline layered silicates, are selected in a subsequent step with further ingredients of washing or cleaning agents, preferably with impregnating agents from the group of ethoxylated nonionic surfactants, mixtures of non-ionic and anionic surfactants, paste-like aqueous nonionic and / or anionic surfactants, the water possibly being subsequently dried off, and silicone oils and paraffin oils, in particular with nonionic surfactants, acted upon. Following this impregnation, the builder components can then additionally be powdered off with powdery solids, in particular with powdery crystalline layered silicates.
Gegenstand der Erfindung ist in einer weiteren Ausführungsform der Erfin¬ dung ein Wasch- oder Reinigungsmittel, welches die erfindungsgemäßen Ge¬ rüststoffkomponenten enthält. Vorzugsweise enthalten diese Mittel die er- findungsgemäßen Gerüststoffko ponenten in Mengen von 10 bis 70 Gew.-% und insbesondere in Mengen von 20 bis 60 Gew.-%. Insbesondere wenn die Wasch¬ oder Reinigungsmittel weitere übliche anorganische und/oder organische Gerüststoffe enthalten, sind Gehalte an den erfindungsgemäßen Gerüststoff¬ komponenten von 25 bis 50 Gew.-% besonders vorteilhaft. Ansonsten können die Wasch- oder Reinigungsmittel alle üblichen Inhaltsstoffe wie anioni¬ sche, nichtionische, amphotere, kationische und/oder zwitterionische Ten- side, weitere Gerüststoffe wie Zeolith und/oder Phosphate, Schichtsilikate wie Bentonite, Polycarboxylate wie Citrate etc., polymere Polycarboxylate wie Salze von Homo- oder Copolymeren der Acrylsäure, Bleichmittel und Bleichaktivatoren, Vergrauungsinhibitoren wie Celluloseether oder Poly- vinylpyrrolidon, optische Aufheller, Färb- und Duftstoffe sowie Enzyme und Enzymstabilisatoren enthalten. Auch Schauminhibitoren können enthalten sein. Die Mittel können abgesehen von der zugemischten erfindungsgemäßen Gerüststoffkomponente aus einem Basisgranulat oder aus einem Mehrkomponen¬ tengemisch bestehen, wobei Mehrkomponentengemische von Vorteil sein kön¬ nen. Insbesondere werden dabei Enzymgranulate und beispielsweise Bleich- aktivatorgranulate, aber auch Schauminhibitorgranulate oder einzelne Be¬ standteile wie Natriu carbonat, Natriumsilikat oder Polycarboxylat nach¬ träglich zugemischt. Die einzelnen Komponenten können durch Sprühtrock¬ nung, Granulierung, Extrusion oder andere herkömmliche Techniken herge¬ stellt werden. Insbesondere ist es bevorzugt, daß die Mittel insgesamt ein Schüttgewicht oberhalb 650 g/1, vorzugsweise oberhalb 700 g/1 aufweisen. Durch den Einsatz der erfindungsgemäßen Gerüststoffkomponenten in hohen Mengen können auch Wasch- oder Reinigungsmittel mit Schüttgewichten ober¬ halb 800 g/1 hergestellt werden, ohne daß diese Mittel zur Entmischung neigen. Diese Mittel eignen sich ebenfalls zu Konzentraten mit hohen Ten- sidgehalten. So kann beispielsweise ein hoher Aniontensidgehalt durch Zu- ischung eines hochkonzentrierten Aniontensid-Compounds, das beispiels¬ weise durch Sprühtrocknung, Sprühneutralisation oder durch Granulierung und gleichzeitige Trocknung in einer Wirbelschicht erhalten wurde, und ein hoher Niotensidgehalt durch Zumischung der erfindungsgemäßen Gerüststoff¬ komponenten mit hohen Niotensidanteilen erreicht werden. Wasch- oder Rei¬ nigungsmittel mit 15 bis 40 Gew.-%, insbesondere mit 18 oder 20 bis 35 Gew.-% anionischen und nichtionischen Tensiden sind dabei bevorzugt. In einer weiteren Ausführungsform der Erfindung werden die erfindungsgemäß hergestellten walzenkompaktierten, vorzugsweise mit Niotensiden beauf¬ schlagten Granulate zu extrudierten Granulaten, welche gegebenenfalls hochkonzentrierte Aniontensid-Compounds enthalten und vorzugsweise Nio- tensid-ar bis insbesondere Niotensid-frei sind, hinzugemischt. In a further embodiment of the invention, the invention relates to a washing or cleaning agent which contains the builders components according to the invention. These agents preferably contain the Gerüststoffko components according to the invention in amounts of 10 to 70 wt .-% and in particular in amounts of 20 to 60 wt .-%. In particular, if the washing or cleaning agents contain further conventional inorganic and / or organic builders, contents of 25 to 50% by weight of the builders components according to the invention are particularly advantageous. Otherwise, the washing or cleaning agents can contain all the usual ingredients such as anionic, nonionic, amphoteric, cationic and / or zwitterionic surfactants, other builders such as zeolite and / or phosphates, layered silicates such as bentonites, polycarboxylates such as citrates etc., polymeric polycarboxylates such as Contain salts of homo- or copolymers of acrylic acid, bleaching agents and bleach activators, graying inhibitors such as cellulose ethers or polyvinylpyrrolidone, optical brighteners, dyes and fragrances, and enzymes and enzyme stabilizers. Foam inhibitors can also be included. Apart from the admixed builder component according to the invention, the agents can consist of a basic granulate or of a multicomponent mixture, whereby multicomponent mixtures can be advantageous. In particular, enzyme granules and, for example, bleach activator granules, but also foam inhibitor granules or individual components such as sodium carbonate, sodium silicate or polycarboxylate, are subsequently mixed in. The individual components can be produced by spray drying, granulation, extrusion or other conventional techniques. In particular, it is preferred that the agents have a bulk density above 650 g / 1, preferably above 700 g / 1. By using the builder components according to the invention in large quantities, detergents or cleaning agents with bulk densities above 800 g / l can also be produced without these agents tending to separate. These agents are also suitable for concentrates with high surfactant contents. For example, a high anionic surfactant content can be obtained by adding a highly concentrated anionic surfactant compound obtained, for example, by spray drying, spray neutralization or by granulation and simultaneous drying in a fluidized bed, and a high nonionic surfactant content by admixing the builder components with high nonionic surfactant components can be achieved. Detergents or cleaning agents with 15 to 40% by weight, in particular with 18 or 20 to 35% by weight, anionic and nonionic surfactants are preferred. In a further embodiment of the invention, the invention Roll-compacted granules, preferably coated with nonionic surfactants, are added to extruded granules which may contain highly concentrated anionic surfactant compounds and are preferably non-surfactant-ar to, in particular, non-surfactant-free.
BeispieleExamples
Kristalline Schichtsilikate des Typs SKS δ(R) (HT-Natriumdisilikat, Han¬ delsprodukt der Hoechst AG, Deutschland) oder die unten angegebenen Mi¬ schungen aus SKS 6(R) und den anorganischen bzw. organischen Salzen mehr- basiger Säuren wurden auf einer Walzenpresse des Typs WR 50 N/75 (Alexan¬ derwerk AG, Deutschland) bei den unten angegebenen Temperaturen zu Schul- pen von ca. 1 mm Stärke verpreßt. Nach der Zerkleinerung zu einem Granulat mit einem mittleren Kornspektrum von 0,1 bis 1,6 mm wurden Produkte mit den unten angegebenen Schüttgewichten erhalten. Die in der Tabelle ange¬ gebenen Lösegeschwindigkeiten wurden für die Siebfraktion 0,6 bis 0,8 m nach folgendem Test ermittelt:Crystalline layered silicates of the type SKS δ ( R ) (HT sodium disilicate, commercial product from Hoechst AG, Germany) or the mixtures of SKS 6 ( R ) and the inorganic or organic salts of polybasic acids given below were mixed on a Roll press of the type WR 50 N / 75 (Alexanderwerk AG, Germany) pressed at the temperatures given below to form shoulders of approx. 1 mm thickness. After comminution into granules with an average particle size range of 0.1 to 1.6 mm, products with the bulk densities specified below were obtained. The dissolving speeds given in the table were determined for the sieve fraction 0.6 to 0.8 m according to the following test:
In einem doppelwandigen und thermostatisierten 1-1-Gefäß wurden 500 ml demineralisiertes Wasser (20°C) eingefüllt, der Schrägblattrührer mit einer Drehzahl von 900 Umdrehungen pro Minute eingeschaltet und die Leit- fähigkeitsmeßzelle eingetaucht. Danach wurden 5 g der Gerüststoffkompo- nente zugegeben. Die Änderung der Leitfähigkeit wurde über einen Schreiber festgehalten. Die Messung erfolgte, bis kein Anstieg der Leitfähigkeit mehr feststellbar war. Die Zeit zum Erreichen der Leitfähigkeitskonstanz ist die Lösezeit der Gerüststoffkomponente (100 %). Die Lösezeiten bei 80 iger, 90%iger und 95%iger Auflösung wurden rechnerisch ermittelt. 500 ml of demineralized water (20 ° C.) were poured into a double-walled and thermostated 1-1 vessel, the inclined blade stirrer was switched on at a speed of 900 revolutions per minute and the conductivity measuring cell was immersed. 5 g of the builder component were then added. The change in conductivity was recorded by a recorder. The measurement was carried out until there was no increase in conductivity. The time to reach constant conductivity is the dissolving time of the builders component (100%). The dissolution times at 80%, 90% and 95% resolution were calculated.
Tabelle: Walzenkompaktierung der Zusammensetzungen VI bis V3 bei 20 °C (zum Vergleich) und Ml bis M3 bei 60 °C (erfindungsgemäß)Table: Roll compacting of compositions VI to V3 at 20 ° C (for comparison) and Ml to M3 at 60 ° C (according to the invention)
VI Ml V2 M2 V3 M3VI Ml V2 M2 V3 M3
SKS 600 100 100 80 80 80 80 in Gew.-%SKS 600 100 100 80 80 80 80 in% by weight
Natrium¬ sulfat — — 20 20 — — in Gew.-%Sodium sulfate - - 20 20 - - in% by weight
Natriu - citrat — — — — 20 20 in Gew.-%Natriu - citrate - - - - 20 20 in% by weight
Preßdruck in kN/cm 14 14 17 17 17 17Pressure in kN / cm 14 14 17 17 17 17
Lösezeit in minDissolving time in min
80 % 3,3 1,9 1,4 0,8 1,0 0,880% 3.3 1.9 1.4 0.8 1.0 0.8
90 % 5,6 3,5 3,0 1,4 2,0 1,890% 5.6 3.5 3.0 1.4 2.0 1.8
95 % 7,9 5,3 4,6 2,1 3,0 2,4 95% 7.9 5.3 4.6 2.1 3.0 2.4

Claims

Patentansprüche claims
1. Verfahren zur Herstellung einer Gerüststoffkomponente, welche minde¬ stens 10 Gew.-% kristalline Schichtsilikate der Formel NaMSix02χ+ι •yH2θ enthält, wobei M Natrium oder Wasserstoff bedeutet, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist, durch Walzenkompak¬ tierung bei Preßdrucken bis 50 kN/cm Walzenlänge, dadurch gekennzeich¬ net, daß die kristallinen Schichtsilikate und gegebenenfalls weitere übliche Inhaltsstoffe von Wasch- oder Reinigungsmitteln bei Walzentem¬ peraturen zwischen 35 und 120 °C kompaktiert werden.1. A process for producing a builder component which contains at least 10% by weight of crystalline phyllosilicates of the formula NaMSi x 02χ + ι • yH2θ, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number is from 0 to 20, by roller compaction at compression pressures of up to 50 kN / cm roller length, characterized in that the crystalline layered silicates and, if appropriate, other conventional ingredients of detergents or cleaning agents are compacted at roller temperatures between 35 and 120 ° C. .
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Walzenkom¬ paktierung von kristallinen Schichts likaten allein oder von Mischun¬ gen aus kristallinen Schichtsilikaten und blichen weiteren Inhalts¬ stoffen von Wasch- oder Reinigungsmittelr.. wobei der Gehalt der Mi¬ schung an kristallinen Schichtsilikaten 50 bis 99,5 Gew.-%, vorzugs¬ weise 60 bis 90 Gew.-%, beträgt, bei Walzentemperaturen zwischen 40 und 100 °C, vorzugsweise zwischen 45 und 90 °C durchgeführt wird.2. The method according to claim 1, characterized in that the Walzenkom¬ paktierung of crystalline layered likate alone or of Mischun¬ gene of crystalline layered silicates and usual other ingredients of detergents or cleaners. . the crystalline layered silicate content of the mixture being 50 to 99.5% by weight, preferably 60 to 90% by weight, carried out at roller temperatures between 40 and 100 ° C., preferably between 45 and 90 ° C. becomes.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Wal¬ zenkompaktierung bei Preßdrucken zwischen 7 und 30 kN/cm Walzenlänge, vorzugsweise bei Preßdrucken zwischen 10 und 25 kN/cm Walzenlänge durchgeführt wird.3. The method according to claim 1 or 2, characterized in that the roller compacting is carried out at pressures between 7 and 30 kN / cm roll length, preferably at pressures between 10 and 25 kN / cm roll length.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß eine Mischung eingesetzt wird, die kristalline Schichtsilikate und Salze anorganischer und/oder organischer Säuren, insbesondere mehrba- siger Säuren, enthält, wobei der Gehalt der Mischung an diesen Salzen vorzugsweise 0,5 bis 50 Gew.-% und insbesondere 10 bis 40 Gew.-% be¬ trägt.4. The method according to any one of claims 1 to 3, characterized in that a mixture is used which contains crystalline phyllosilicates and salts of inorganic and / or organic acids, in particular polybasic acids, the content of the mixture of these salts preferably being 0 , 5 to 50% by weight and in particular 10 to 40% by weight.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß eine Mischung eingesetzt wird, die kristalline Schichtsilikate und herkömmliche Gerüststoffe wie Phosphate und/oder Zeolithe enthält, wobei der Gehalt an Zeolith vorzugsweise 0,5 bis 50 Gew.-% und insbe¬ sondere 1 bis 20 Gew.-% beträgt. 5. The method according to any one of claims 1 to 4, characterized in that a mixture is used which contains crystalline layered silicates and conventional builders such as phosphates and / or zeolites, the content of zeolite preferably 0.5 to 50 wt .-% and is in particular 1 to 20% by weight.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß eine Mischung eingesetzt wird, welche 0 bis 20 Gew.-%, vorzugs¬ weise 0 bis 10 Gew.-% weitere übliche Inhaltsstoffe von Wasch- oder Reinigungsmitteln enthält.6. The method according to any one of claims 1 to 5, characterized in that a mixture is used which contains 0 to 20 wt .-%, preferably 0 to 10 wt .-% of other usual ingredients of detergents or cleaning agents.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß als kristalline Schichtsilikate Disilikate und insbesondere ß-Na¬ triumdisilikat und/oder fr-Natriumdisilikat eingesetzt werden.7. The method according to any one of claims 1 to 6, characterized in that disilicates and in particular ß-sodium disilicate and / or fr-sodium disilicate are used as crystalline sheet silicates.
8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß als anorganische und/oder organische Salze mehrbasiger Säuren Sul¬ fat und/oder Citrat eingesetzt werden.8. The method according to any one of claims 1 to 7, characterized in that Sul¬ fat and / or citrate are used as inorganic and / or organic salts of polybasic acids.
9. Verfahren nach Anspruch 7 und 8, dadurch gekennzeichnet, daß eine Wal¬ zenkompaktierung einer Mischung, bestehend aus 70 bis 90 Gew.-% ß-Na¬ triumdisilikat und/oder S'-Natriumdisilikat und aus 10 bis 30 Gew.-% Natriumsulfat und/oder Natriumeitrat, bei Walzentemperaturen zwischen 50 und 70 °C und bei Preßdrucken zwischen 12 und 20 kN/cm Walzenlänge durchgeführt wird.9. The method according to claim 7 and 8, characterized in that a roller compacting a mixture consisting of 70 to 90 wt .-% ß-sodium disilicate and / or S'-sodium disilicate and from 10 to 30 wt .-% Sodium sulfate and / or sodium citrate, at roll temperatures between 50 and 70 ° C and at pressures between 12 and 20 kN / cm roll length is carried out.
10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß das Schülpenband durch übliche Mahlung in Granulate mit einem Kornspektrum von 0,05 mm bis etwa 2 mm, vorzugsweise mit einem Korn¬ spektrum, das zu mindestens 70 Gew.-% aus Granulaten mit einem Teil¬ chendurchmesser zwischen 0,1 und 1,6 mm besteht, eingestellt und Fein¬ kornanteile mit Granulatdurchmessern unterhalb 0,05 mm in die Kom¬ paktierung und Grobkornanteile mit Granulatdurchmessern oberhalb 2 mm in die Mahlung zurückgeführt werden.10. The method according to any one of claims 1 to 9, characterized in that the Schülpenband by conventional grinding in granules with a grain size range of 0.05 mm to about 2 mm, preferably with a grain size spectrum that at least 70 wt .-% consists of granules with a particle diameter between 0.1 and 1.6 mm, adjusted and fine particles with granule diameters below 0.05 mm are returned to the compacting and coarse particles with granule diameters above 2 mm are returned to the grinding.
11. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß eine granuläre Gerüststoffkomponente mit einem Schüttgewicht zwi¬ schen 800 und 1100 g/1 erhalten wird.11. The method according to any one of claims 1 to 10, characterized in that a granular builder component with a bulk density between 800 and 1100 g / 1 is obtained.
12. Verfahren nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß die erhaltenen granulären Gerüststoffkomponenten, welche vorzugs¬ weise aus 100 Gew.-% kristallinen Schichtsilikaten bestehen, in einem anschließenden Schritt mit weiteren Inhaltsstoffen von Wasch- oder Reinigungsmitteln, insbesondere mit nichtionischen Tensiden, beauf¬ schlagt werden.12. The method according to any one of claims 1 to 11, characterized in that the granular builders components obtained, which preferably consist of 100 wt .-% crystalline layered silicates, in one subsequent step with further ingredients of detergents or cleaning agents, in particular with nonionic surfactants.
13. Verfahren nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß die erhaltenen walzenkompaktierten, vorzugsweise mit nicht¬ ionischen Tensiden beaufschlagten Granulate zu extrudierten Granula¬ ten, welche gegebenenfalls hochkonzentrierte Aniontensid-Compounds enthalten und vorzugsweise Niotensid-arm bis insbesondere Niotensid- frei sind, hinzugemischtjverden.13. The method according to any one of claims 1 to 12, characterized in that the roller-compacted granules obtained, preferably loaded with non-ionic surfactants, to extruded granules which optionally contain highly concentrated anionic surfactant compounds and preferably low in nonionic surfactants and in particular free of nonionic surfactants are mixed in.
14. Wasch- oder Reinigungsmittel, enthaltend Gerüststoffkomponenten gemäß einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, daß es die Ge¬ rüststoffkomponenten in Mengen von 10 bis 70 Gew.-%, vorzugsweise in Mengen von 20 bis 60 Gew.-% und insbesondere in Mengen von 25 bis 50 Gew.-% sowie gegebenenfalls weitere übliche anorganische und/oder or¬ ganische Gerüststoffe enthält. 14. washing or cleaning agent containing builder components according to one of claims 1 to 13, characterized in that it the Ge builder components in amounts of 10 to 70 wt .-%, preferably in amounts of 20 to 60 wt .-% and in particular in amounts of 25 to 50% by weight and optionally further conventional inorganic and / or organic builders.
EP94925465A 1993-09-01 1994-08-22 Builder for washing or cleaning products Expired - Lifetime EP0716682B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4329394 1993-09-01
DE4329394A DE4329394B4 (en) 1993-09-01 1993-09-01 Builder component for detergents or cleaners
PCT/EP1994/002778 WO1995006708A1 (en) 1993-09-01 1994-08-22 Builder for washing or cleaning products

Publications (2)

Publication Number Publication Date
EP0716682A1 true EP0716682A1 (en) 1996-06-19
EP0716682B1 EP0716682B1 (en) 1997-10-15

Family

ID=6496503

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94925465A Expired - Lifetime EP0716682B1 (en) 1993-09-01 1994-08-22 Builder for washing or cleaning products

Country Status (7)

Country Link
EP (1) EP0716682B1 (en)
JP (1) JPH09501979A (en)
KR (1) KR960705019A (en)
AT (1) ATE159280T1 (en)
DE (2) DE4329394B4 (en)
ES (1) ES2109726T3 (en)
WO (1) WO1995006708A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19525197A1 (en) * 1995-07-11 1997-01-16 Hoechst Ag Granular detergent builder
DE19700775A1 (en) * 1997-01-13 1998-07-16 Henkel Kgaa Process for the production of washing and cleaning active surfactant granules containing anionic surfactants
DE19756696A1 (en) 1997-12-19 1999-07-01 Clariant Gmbh Detergent and cleaning agent components containing layered silicate

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3624336A1 (en) * 1986-07-18 1988-01-28 Henkel Kgaa METHOD FOR THE PRODUCTION OF GIANT ALKALINE CLEANING AGENTS BY COMPACTING GRANULATION
DE3633519A1 (en) * 1986-10-02 1988-04-14 Henkel Kgaa METHOD FOR THE PRODUCTION OF GIANT, STABLE FOAM INHIBITOR CONCENTRATES BY COMPACTING GRANULATION
CA2024966C (en) * 1989-10-25 1995-07-18 Gunther Schimmel Process for producing sodium silicates
GB9108639D0 (en) * 1991-04-23 1991-06-12 Procter & Gamble Particulate detergent compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9506708A1 *

Also Published As

Publication number Publication date
DE59404364D1 (en) 1997-11-20
KR960705019A (en) 1996-10-09
ATE159280T1 (en) 1997-11-15
WO1995006708A1 (en) 1995-03-09
DE4329394A1 (en) 1995-03-02
EP0716682B1 (en) 1997-10-15
DE4329394B4 (en) 2006-11-02
ES2109726T3 (en) 1998-01-16
JPH09501979A (en) 1997-02-25

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