EP0561656B1 - Builder auf Basis von Silikat und anorganischer Verbindung - Google Patents

Builder auf Basis von Silikat und anorganischer Verbindung Download PDF

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Publication number
EP0561656B1
EP0561656B1 EP93400359A EP93400359A EP0561656B1 EP 0561656 B1 EP0561656 B1 EP 0561656B1 EP 93400359 A EP93400359 A EP 93400359A EP 93400359 A EP93400359 A EP 93400359A EP 0561656 B1 EP0561656 B1 EP 0561656B1
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EP
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Prior art keywords
silicate
alkali metal
order
equal
carbonate
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EP93400359A
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English (en)
French (fr)
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EP0561656A1 (de
Inventor
Patrick Boittiaux
Daniel Joubert
Pascal Taquet
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Rhodia Chimie SAS
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Rhone Poulenc Chimie SA
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates

Definitions

  • the present invention relates to a "builder" agent in a structured form consisting of a solution of alkali metal silicates rich in silicon atoms in Q 2 and Q 3 form , this solution being in the presence of a mineral product other inert with respect to silicate.
  • This builder agent is intended for detergent compositions, in particular for powdered detergents, in particular for washing machines or dishwashers.
  • the invention also relates to cogranules of hydrated alkali metal silicates and alkali metal carbonates.
  • builder is understood to mean any active adjuvant which improves the performance of the surfactants of a detergent composition.
  • the builder must have a so-called "softening" effect on the water used for washing. It must therefore eliminate the calcium and magnesium which are present in the water in the form of soluble salts, and in the stains of the linen in more or less soluble complex forms.
  • the elimination of calcium and magnesium can be done either by complexation, in the form of soluble species, or by ion exchange, or by precipitation. If precipitation is involved, it must be checked to avoid encrustations on the laundry or on the elements of washing machines.
  • This precipitation control is in particular obtained by water-soluble polymers having an affinity for calcium and magnesium.
  • the builder adds to the emulsifying effect of surfactants vis-à-vis fatty stains a dispersing effect vis-à-vis "pigmentary" stains, such as metal oxides, clays, silica, various dusts, humus, limestone, soot.
  • This dispersing effect is generally obtained thanks to the presence of polyanions, providing a high density of negative charges at the interfaces.
  • the builder provides an ionic strength favorable to the functioning of the surfactants, in particular by increasing the size of the micelles.
  • Silicates have long been regarded as good detergency builders, but are currently used less in phosphate-free compositions for washing machines.
  • the silicates most used in this application are those having a SiO 2 / Na 2 O molar ratio of between 1.6 and 2.7.
  • the concentrated commercial solutions are most often prepared from completely amorphous silicate called “glassy”, also called “water glass”.
  • the concentrated silicate solutions are introduced by the detergent formulator into the aqueous suspension (slurry) containing the other constituents of the detergent.
  • the slurry is then spray dried.
  • this powdered silicate which contains only 19 to 22% by weight of associated water (relative to the finished product), has only weak builder properties.
  • this powdered silicate in solution essentially generates monomeric silicic species of formula Si (OX) 4 , where X represents H or Na, having no builder effect.
  • monomeric species can only re-associate with each other to form polyanions if the silicate concentration is at least 50 to 500 g / liter and this slowly.
  • silicate concentrations as well as the slow polymerization kinetics of the monomeric species are not compatible with the conditions and the durations of washing in a washing machine.
  • Patent application EP-A-450 989 describes a process for the preparation of granulates of hydrated alkali metal silicates by spraying water or an aqueous solution of alkali metal silicates on a moving bed of particles of hydrated metal silicates alkaline scrolling in a thin layer in a device of the rotating plate type at room temperature, possible densification and drying. These granules can be used as "builder" agents for detergent compositions.
  • Patent application JP-A-59,157,198 describes the preparation of low density "builder” granules, by fluidization of "builder” particles (especially sodium carbonate) with hot air at 200 ° C., with spraying. of a sodium silicate binder solution containing a little "builder”.
  • US-A-2,909,490 describes dry granular solid compositions combining sodium tripolyphosphate and certain silicate solutions; the amount of sodium tripolyphosphate represents at least 68.5% of the weight of said compositions expressed on a dry basis.
  • detergency builders are mixtures of alkaline hydrated silica pigment and alkali metal carbonate and / or bicarbonate (US-A-3,886,079).
  • silicon atoms in Q 2 and Q 3 form is a representation of the degree of association of the silicon atoms with each other;
  • Q 2 means that each silicon atom participates in two -Si-O-Si- bonds, the two remaining bonds being a termination -Si-OX where X is an alkali metal or H;
  • Q 3 means that each silicon atom participates in three -Si-O-Si- bonds, the remaining bond being a -Si-OX termination.
  • a "builder” agent consisting of an alkali metal silicate with an SiO 2 / Na 2 O ratio of the order of 1.6 to 3.5 and of an inert inorganic support with respect to the silicate, said agent having a water weight ratio remaining associated with the silicate / silicate expressed as dryness greater than or equal to 40/100.
  • This agent can be obtained by adsorption and / or absorption of a concentrated aqueous solution of alkali metal silicate with a SiO 2 / Na 2 O ratio of the order of 1.6 to 3.5 rich in species Q 2 and Q 3 on said inorganic support, said support being present in an amount such that the amount of water remaining associated with the silicate corresponds to a weight ratio of water remaining associated with the silicate / silicate expressed in dry matter greater than or equal to 40/100.
  • the support generally represents from 55 to 95% of the weight of said agent expressed in dry terms.
  • the “builder” agent in a structured form for a detergent composition which is the subject of the invention, consisting of an aqueous solution of an alkali metal silicate with a SiO 2 / M 2 O molar ratio of about 1, 6 to 4 and a mineral product other than said silicate, inert with respect to said silicate and miscible in said silicate solution, is characterized in that said mineral product other than said silicate represents from 5 to less than 55% of the total weight expressed in dry and the weight ratio of water remaining associated with the silicate / silicate expressed in dry is greater than or equal to 33/100 and less than or equal to 120/100, preferably greater than or equal to 36/100, M representing a alkali metal and the water remaining associated with the silicate being water not combined with the other mineral product.
  • inert chemically inert
  • the mineral products inert with respect to silicate and miscible in the aqueous solution of silicates are preferably water-soluble.
  • these products there may be mentioned in particular: alkali metal carbonates, sodium sulfate, sodium borate, sodium perborate, sodium metasilicate, phosphates or polyphosphates such as trisodium phosphate, sodium tripolyphosphate ... , these products being present alone or as a mixture between them.
  • Use is preferably made of products having a detergency activity, and more particularly sodium carbonate.
  • the mineral product represents from 5 to less than 55%, preferably from 20 to 40%, of the total weight expressed in dry, that is to say of the sum of the weights of the solution expressed in dry and of the mineral product.
  • the mineral product is either introduced directly into the aqueous solution of alkali metal silicate, or is introduced into water and then mixed, subsequently, with the aqueous solution of alkali metal silicate.
  • Said silicate may have a SiO 2 / M 2 O molar ratio of the order of 1.6 to 4, preferably of the order of 1.8 to 3.5.
  • said "builder” agent consists of an aqueous solution of about 10 to 60%, preferably about 35 to 50% by weight of dry extract of a metal silicate alkaline, especially sodium or potassium.
  • the concentrated solution of alkali metal silicate used in the "builder” agent is preferably obtained by water-solubilization of "soluble glasses” in an autoclave under pressure at 140 ° C., then optional dilution; it can also be obtained by other known means, such as direct attack on sand with caustic soda in concentrated solution.
  • water associated with the silicate is understood to mean the water of said aqueous solution which is not combined with the mineral product, in particular which is not in the form of a crystallized hydrate.
  • the weight ratio of water remaining associated with the silicate / silicate expressed in terms of dryness which must be greater than or equal to 33/100, preferably 36/100, corresponds to the need to be in the presence of silicates in polyanionic forms. It is within the reach of those skilled in the art to set the upper limit of this ratio, this limit corresponding, of course, to the limits for which a silicate is kept in powder form with fluid flow ("free flowing"), it is to say usable in detergency. To fix the ideas, the weight ratio of water remaining associated with silicate / silicate expressed as dry must be less than or equal to about 120/100.
  • the high silicate content in the products of the present invention makes it possible in particular to obtain very satisfactory "anti-encrustation" performance on the laundry or on the elements of the washing machines.
  • the builder agent of the present invention can in particular be prepared by contacting an aqueous solution (A) consisting of a mixture of a concentrated aqueous solution of an alkali metal silicate (1) of molar ratio SiO 2 / M 2 O of the order of 1.6 to 4, preferably of the order of 1.8 to 3.5, exhibiting a dry extract content of silicate of the order of 10 to 60% , preferably of the order of 35 to 50%, rich in silicon atoms in the form Q 2 and Q 3 , and of another mineral product (2) dissolved, the mineral product being inert with respect to the silicate and miscible in the aqueous solution (1) and representing from 5 to less than 55% by total weight expressed on a dry basis, with a compound (B) of composition identical to the aqueous solution (A) cited above, so that the weight ratio of water remaining associated with total silicate / total silicate expressed in dry conditions, after contacting, is greater than or equal to 33/100, preferably 36/100, and less than or equal to 120
  • the aqueous solution (A) was prepared by any means known per se. It can in particular be prepared by introducing the mineral product, in the form of powder or liquid, into the aqueous silicate solution.
  • compound (B) of composition identical to the aqueous solution (A) is meant any compound comprising an alkali metal silicate and a mineral product as defined above, the mineral product representing from 5 to less than 55% of the total weight expressed in sec.
  • Said compound (8) preferably has a water weight ratio remaining associated with the silicate / silicate expressed as dryness greater than or equal to 33/100, preferably 36/100.
  • This compound (B) can be obtained by any means known per se. Thus, it can in particular be obtained by drying a solution identical to the aqueous solution (A). This drying is preferably controlled so as to keep the desired proportions of water associated with the silicate, that is to say that the weight ratio of water remaining associated with the silicate / silicate expressed as dry is greater than or equal to 33/100, preferably 36/100.
  • the concentrated aqueous solution of alkali metal silicate preferably has a water weight ratio remaining associated with the silicate / silicate expressed in dry matter greater than or equal to 33/100, preferably 36/100.
  • the contacting operation can be carried out by adding, in particular by spraying (A) onto (B), in any known mixer with high shear, in particular of the LODIGE® type, or in the granulation tools (drum, plate) to a temperature of the order of 20 to 95 ° C, preferably of the order of 70 to 95 ° C.
  • the mineral products which can be used are those already mentioned previously.
  • the quantity and concentration of the aqueous solution (A) to be used depends on the absorbing and / or adsorbing power of the mineral products present in the solution (A) and the compound (B) with respect to the silicate present in the solution (A) and the compound (B), taking into account a possible possibility for said mineral products to form in particular crystallizable hydrates;
  • the level of water not associated with the silicate which may be in the form of a hydrate in the support can be determined in a known manner by differential thermal analysis or by quantitative X-ray diffraction.
  • the water possibly combined with the support in forms other than hydrates can be determined by appropriate physicochemical methods (thermoporosimetry, thermogravimetry, proton NMR, IR).
  • the limit of absorbent and / or adsorbent capacity of said mineral products can be determined according to known methods, for example by measuring the evolution of the angle at the base of the landslide as a function of the rate of addition of the solution. silicate.
  • alkali metal silicate solutions in the form adsorbed and / or absorbed on an alkali metal carbonate and which are in the form of cogranules of hydrated alkali metal silicate and alkali metal carbonate are builder agents of the invention particularly efficient.
  • cogranules can be used as a simple and efficient means of supplying silicate and carbonate in the detergent compositions.
  • particles of composition identical to the spray mixture are meant particles comprising an alkali metal silicate and an alkali metal carbonate representing from 5 to less than 55% of the total weight expressed as dry. These said particles preferably have a weight ratio of water remaining associated with the silicate / silicate expressed in dry matter greater than or equal to 33/100, preferably 36/100, and less than or equal to 120/100.
  • These particles can be obtained by any means known per se.
  • They can in particular be obtained by drying a solution identical to the aqueous solution consisting of silicate and alkali metal carbonate mentioned above. This drying is preferably controlled so as to keep the desired proportions of water associated with the silicate, that is to say that the weight ratio of water remaining associated with the silicate / silicate expressed as dry is greater than or equal to 33/100, of preferably 36/100, and less than or equal to 120/100.
  • the rolling bed of particles of composition identical to the sprayed mixture can also be obtained by starting initially with a dry mixture of carbonate and silicate of ratio expressed by weight carbonate / silicate identical to the sprayed solution, until this bed is completely renewed by the co-granules obtained (recycling).
  • the concentrated aqueous solution of alkali metal silicate preferably has a weight ratio of water associated with the silicate / silicate expressed as dryness greater than or equal to 33/100, preferably 36 / 100.
  • alkali metal silicates and carbonates mention may preferably be made of those of sodium and potassium, and very particularly those of sodium.
  • steps (a). and (b). the cogranules obtained in (a) are subjected. to a densification operation.
  • the spraying of the aqueous solution based on the silicate / carbonate mixture is carried out at a temperature of the order of 20 to 95 ° C, preferably of the order of 70 to 95 ° C; this can be promoted by the joint introduction (for example using a two-fluid nozzle) of pressurized air at a temperature of the same order.
  • the carbonates used can be those of common qualities.
  • the carbonates which dissolve easily and which have a high adsorbent / absorbent capacity are used.
  • these particles of carbonate / silicate mixture may be present small quantities (less than 10% of the weight of the cogranules) of the other particles, such as antireepositive polymers (carboxymethyl - cellulose), enzymes, polyacrylates, commonly used in the detergency field, having a diameter and a density close to those of the carbonate / silicate mixture particles.
  • antireepositive polymers carboxymethyl - cellulose
  • enzymes polyacrylates
  • polyacrylates commonly used in the detergency field, having a diameter and a density close to those of the carbonate / silicate mixture particles.
  • the device used to carry out the co-granulation spraying operation can be any rotary device of the rotating plate, bezel, rotating drum, mixer-granulator type.
  • a first preferred embodiment of these cogranules consists in using a rotary granulator allowing the particles to travel in a thin layer.
  • the beziers having an axis of rotation inclined relative to the horizontal at an angle greater than 20 °, preferably greater than 40 °, are particularly well suited; their geometry can be very diverse: frusto-conical, flat, stepped, a combination of these three forms.
  • a second preferred embodiment of these cogranules consists in using a rotary drum, the angle of inclination of which is at least 3% and preferably at least 5%.
  • the particles based on a carbonate / silicate mixture run at a temperature of the order of 15 to 120 ° C and very particularly of the order of 15 to 30 ° C.
  • the quantities of solution based on silicate / carbonate mixture to be sprayed and of particles based on silicate / carbonate mixture to be used correspond to a liquid flow rate / particle flow rate (wetting ratio) which can range from 0.05 to 0.8 l / kg, preferably 0.1 to 0.5 l / kg and very particularly 0.15 to 0.3 l / kg, these values being expressed as sodium salts.
  • the flow rate of the sprayed solution, the speed of movement of particles as well as the thickness of the layer of particles in movement are such that each particle absorbs liquid and agglomerates with the other particles with which it comes into contact in order to obtain plastic granules and not a paste.
  • the speed of movement of the particles and the thickness of the layer are regulated by the rate of introduction of the particles into the granulation device and by the characteristics of the latter.
  • the residence time of the particles in a device of the plate or drum type is generally of the order of 15 to 40 minutes.
  • the densification operation can be carried out at ambient temperature by rolling in a rotary device the cogranules obtained in step (a), that is to say in the granulation step.
  • This device can be dependent or independent of that of granulation.
  • This densification step can advantageously be carried out by introduction and stay of the cogranules in a rotary drum.
  • the angle of inclination of the latter is at least 3%, preferably at least 5%.
  • the dimensions of this drum, its speed of rotation and the residence time of the cogranules depend on the density sought; the residence time is generally of the order of 20 minutes to 3 hours, preferably of the order of 20 to 90 minutes.
  • Mixer-granulators are also well suited to this densification operation.
  • the cogranulation and densification operations can therefore be carried out in the same device, for example in a stepped bezel, the densification of the cogranules being obtained by rolling said cogranules on the last steps of the apparatus; similarly, these two operations can be carried out in a drum with two sections.
  • the cogranules can therefore be dried by any known means.
  • a particularly effective method is drying in a fluidized bed using an air stream at a temperature of the order of 40 to 90 ° C, preferably from 60 to 80 ° C. This operation is carried out for a period depending on the air temperature, the water content of the cogranules at the outlet of the granulation device and that desired of the dried cogranules, as well as the fluidization conditions; a person skilled in the art knows how to adapt these different conditions to the product sought.
  • the weight ratio of water remaining associated with the silicate / silicate expressed as dry must be less than or equal to approximately 120/100.
  • the dissolution rates of 90% and 95% in water of the cogranules according to the invention are respectively less than 3 minutes and less than 5 minutes.
  • dissolution rate at 90% or 95% in water means the time necessary to dissolve 90% or 95% of product at a concentration of 35 g / l in water at 20 ° C.
  • the builder agent of the invention is used in detergent compositions for dishwashers in an amount of 3 to 90% by weight, preferably from 3 to 70% by weight, of said compositions; the quantities used in the compositions for washing machines are of the order of 3 to 60%, preferably of the order of 3 to 40%, of the weight of said compositions (these quantities are expressed by weight of dry silicate by relative to the composition weight).
  • At least one surfactant is present in the detergent composition in an amount which can range from 8 to 20%, preferably of the order of 10 to 15. %, of the weight of said composition.
  • a solution at 38% by weight of carbonate (expressed as dry silicate and carbonate) is prepared at 80 ° C. by mixing a solution of carbonate in the ratio 2 silicate solution.
  • the dry extract of the mixed solution thus prepared is 37.7%.
  • the granulation of this solution is carried out in a drum with a length of 1300 mm and a diameter of 500 mm which rotates at 20 revolutions per minute.
  • Granulation is initiated from a footboard composed of a ground mixture of light carbonate and atomized silicate of ratio 2.
  • the carbonate / silicate composition of this mixture is that of the mixed solution.
  • Granulation takes place in the first part of the drum where the solution is sprayed, via a ramp, onto the powder bed. Drying takes place in the second part of the drum, fitted with lifters, and swept by hot air against the current.
  • Calcium sequestration capacity 243-249 mg of CaCO 3 per gram of anhydrous product. This sequestration capacity is evaluated as in Example 1.
  • the granulation method is the same as in Example 2, but the granulator operates in an open loop, that is to say it is supplied by the dry atomized carbonate / silicate mixture and the mixed solution but without recycling of the product obtained. . There is also simultaneous drying.
  • Calcium sequestration capacity 245 mg of CaCO 3 per gram of anhydrous product. This sequestration capacity is evaluated as in Example 1.
  • the dirt removal performance test is carried out in a WASCATOR FOM 71 r washing machine.
  • Photometric measurements (measurements of the amount of light reflected by the fabric) make it possible to calculate the percentages of soil removal.
  • the anti-fouling performance test in a washing machine is carried out in a SCHULTESS SUPER 6 DE LUXE drum machine.
  • test pieces which have been washed 25 times are dried: they are weighed and calcined at 900 ° C.
  • The% by weight of ash is measured relative to the weight of the starting test pieces.
  • the granulation system consists of a drum rotating at 40 revolutions per minute identical to that described in Example 2.
  • the outlet diaphragm is adjusted so that the residence time of a particle is of the order of 15 to 20 minutes.
  • the drum is continuously fed at a flow rate of 37 kg / h by a carbonate powder having the same characteristics as that of the powders of Example 2.
  • the cogranules at the outlet of the drum are at room temperature and have a density of 0.68 g / cm3.
  • the cogranules are then densified batchwise for one hour in a rotary drum with smooth walls of diameter 500 mm, length 1300 mm and having an inclination of 5%.
  • the drum rotation speed is 20 rpm.
  • the granules thus obtained are dried in a fluidized bed at a temperature of the order of 65 ° C (temperature of the fluidizing air equal to 70 ° C) for 15 min.
  • Calcium sequestration capacity 285 mg of CaCO 3 per gram of anhydrous product. This sequestration capacity is evaluated as in Example 1.
  • the granules exhibit excellent storage behavior.
  • co-granules are introduced by dry mixing with additives in order to obtain a composition for washing machine identical to that described in Example 4 (with the exception of the co-granule).

Claims (16)

  1. "Builder"-Mittel in strukturierter Form für Waschmittel-Zusammensetzungen, bestehend aus einer wäßrigen Lösung eines Alkalimetallsilikates mit einem molaren Verhältnis SiO2/M2O in der Größenordnung von 1,6 bis 4 und einem anderen mineralischen Produkt als das genannte Silikat, das gegenüber dem genannten Silikat inert und mit der genannten Lösung des Silikates mischbar ist, dadurch gekennzeichnet, daß das genannte mineralische Produkt, das anders ist als das genannte Silikat, 5 % bis weniger als 55 % des Gesamtgewichtes darstellt, ausgedrückt in Trockengewicht, und das Verhältnis des Gewichtes an verbleibendem, mit dem Silikat assoziiertem Wasser/Silikat, ausgedrückt in Trockengewicht, höher oder gleich 33/100 und niedriger oder gleich 120/100, vorzugsweise höher oder gleich 36/100 beträgt, M ein Alkalimetall darstellt und das verbleibende, mit dem Silikat assoziierte Wasser nicht mit dem anderen mineralischen Produkt kombiniert ist.
  2. "Builder"-Mittel nach Anspruch 1, dadurch gekennzeichnet, daß das mineralische Produkt, das anders ist als das genannte Silikat, ein Alkalimetallcarbonat, Natriumsulfat, Natriumborat, Natriumperborat, Natriummetasilikat, ein Phosphat oder Polyphosphat wie Trinatriumphosphat, Natrium-tripolyphosphat ist, wobei diese Produkte allein oder in Mischung vorliegen können.
  3. "Builder"-Mittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das mineralische Produkt, das anders ist als das genannte Silikat, 20 % bis 40 % des Gesamtgewichtes darstellt, ausgedrückt in Trockengewicht.
  4. "Builder"-Mittel nach irgendeinem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß die wäßrige Lösung des Alkalimetallsilikates einen Trockenextrakt an Silikat in der Größenordnung von 10 % bis 60 %, vorzugsweise in der Größenordnung von 35 % bis 50 % aufweist.
  5. "Builder"-Mittel nach irgendeinem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das Verhältnis des Gewichtes an verbleibendem, mit dem Silikat assoziiertem Wasser/Silikat, ausgedrückt in Trockengewicht, niedriger oder etwa gleich 120/100 beträgt.
  6. "Builder"-Mittel nach irgendeinem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das molare Verhältnis SiO2/M2O in der Größenordnung von 1,8 bis 3,5 liegt, wobei M ein Alkalimetall darstellt.
  7. Co-Granulate von hydratisiertem Alkalimetallsilikat mit einem molaren Verhältnis von SiO2/M2O in der Größenordnung von 1,6 bis 4, vorzugsweise in der Größenordnung von 1,8 bis 3,5, und von Alkalimetallcarbonaten, wobei die genannten Carbonate 5 % bis weniger als 55 % des Gesamtgewichtes der genannten Co-Granulate darstellen, ausgedrückt in Trockengewicht, und die Menge des mit dem genannten Silikat assoziierten Wassers derart ist, daß das Verhältnis des Gewichtes an verbleibendem, mit dem Silikat assoziiertem Wasser/Silikat, ausgedrückt in Trockengewicht, höher oder gleich 33/100 und niedriger oder gleich 120/100, vorzugsweise höher oder gleich 36/100 beträgt, M ein Alkalimetall darstellt und das verbleibende, mit dem Silikat assoziierte Wasser nicht mit dem anderen mineralischen Produkt kombiniert ist, wobei die genannten Co-Granulate geeignet sind, durch die folgenden Stufen erhalten zu werden:
    (a). Versprühen einer wäßrigen Lösung bei einer Temperatur in der Größenordnung von 20 °C bis 95 °C, bestehend aus einer Mischung einer wäßrigen Lösung von Alkalimetall mit einem molaren Verhältnis von SiO2/M2O in der Größenordnung von 1,6 bis 4, vorzugsweise in der Größenordnung von 1,8 bis 3,5, die einen Gehalt an Trockenextrakt von Silikat in der Größenordnung von 10 % bis 60 %, vorzugsweise in der Größenordnung von 35 % bis 50 % aufweist, und reich an Siliciumatomen in Form von Q2 und Q3 ist, und aus Alkalimetallcarbonat, wobei dieses Carbonat 5 % bis weniger als 55 % des Gesamtgewichtes darstellt, ausgedrückt in Trockengewicht,
    in einem umgewälzten Bett aus Teilchen mit einer Zusammensetzung, die mit der Zusammensetzung der versprühten Mischung identisch ist, und ablaufend bei einer Temperatur in der Größenordnung von 15 °C bis 120 °C in einer Drehvorrichtung zur Granulation, wobei die Geschwindigkeit des Durchlaufens der Teilchen, die Dicke des rollenden Bettes und der Durchsatz der versprühten Lösung derart sind, daß jedes Teilchen sich in ein plastisches Co-Granulat umwandelt, indem es mit den anderen Teilchen in Kontakt tritt,
    (b). gegebenenfalls Trocknung der genannten, in (a) erhaltenen Co-Granulate bei einer Temperatur in der Größenordnung von 40 °C bis 90 °C,
    wobei diese Stufen in der Weise durchgeführt werden, daß das Verhältnis des Gewichtes an verbleibendem, mit dem Silikat assoziiertem Wasser/Silikat, ausgedrückt in Trockengewicht, höher oder gleich 33/100 und niedriger oder gleich 120/100, vorzugsweise höher oder gleich 36/100 beträgt, die Form Q2 bedeutet, daß jedes Siliciumatom an zwei Bindungen -Si-O-Si- teilnimmt, wobei die beiden verbleibenden Bindungen eine Endgruppe -Si-O-X darstellen, worin X ein Alkalimetall oder Wasserstoff ist, und die Form Q3 bedeutet, daß jedes Siliciumatom an drei Bindungen -Si-O-Si- teilnimmt, wobei die verbleibende Bindung eine Endgruppe -Si-O-X ist.
  8. Co-Granulate nach Anspruch 7, dadurch gekennzeichnet, daß das Alkalimetallsilikat und das Alkalimetallcarbonat dasjenige von Natrium oder Kalium ist und vorzugsweise dasjenige von Natrium.
  9. Co-Granulate nach Anspruch 7 oder 8, dadurch gekennzeichnet, daß die in (a) erhaltenen Co-Granulate zwischen den Stufen (a) und (b) einer Operation der Verdichtung unterzogen werden.
  10. Co-Granulate nach irgendeinem der Ansprüche 7 bis 9, dadurch gekennzeichnet, daß die Teilchen mit einer identischen Zusammensetzung, wie sie die versprühte Mischung aufweist, durch Trocknung einer Lösung erhalten werden, die mit der genannten wäßrigen, aus Alkalimetallsilikat und Alkalimetallcarbonat bestehenden Lösung identisch ist.
  11. Co-Granulate nach irgendeinem der Ansprüche 7 bis 10, dadurch gekennzeichnet, daß die Vorrichtung zur Granulation ein Dreh-Granulator ist, der das Durchlaufen der Teilchen in dünner Schicht gestattet.
  12. Co-Granulate nach irgendeinem der Ansprüche 7 bis 10, dadurch gekennzeichnet, daß der Dreh-Granulator ein Dragierkessel ist.
  13. Co-Granulate nach irgendeinem der Ansprüche 7 bis 10, dadurch gekennzeichnet, daß der Dreh-Granulator eine Trommel ist.
  14. Co-Granulate nach irgendeinem der Ansprüche 7 bis 13, dadurch gekennzeichnet, daß die Mengen der Lösung auf der Basis der zu versprühenden Mischung Silikat/Carbonat und der Teilchen auf der Basis der eingesetzten Mischung Silikat/Carbonat einem Durchsatzverhältnis von Flüssigkeit/Durchsatz der Teilchen entsprechen, das von 0,05 l/kg bis 0,8 l/kg, vorzugsweise von 0,1 l/kg bis 0,5 l/kg betragen kann, wobei diese Werte in Natriumsalz ausgedrückt sind.
  15. Co-Granulate nach irgendeinem der Ansprüche 7 bis 14, dadurch gekennzeichnet, daß die Operation der Verdichtung bei Umgebungstemperatur durch Umwälzen der in der Stufe (a) erhaltenen Co-Granulate in einer Drehvorrichtung durchgeführt wird.
  16. Sphärische Co-Granulate auf der Basis von hydratisiertem Alkalimetallsilikat und Alkalimetallcarbonat, dadurch gekennzeichnet, daß sie aufweisen:
    - ein Alkalimetallsilikat, insbesondere von Natrium oder Kalium mit einem molaren Verhältnis SiO2/M2O in der Größenordnung von 1,6 bis 4, adsorbiert und/oder absorbiert auf einem Alkalimetallcarbonat, wobei dieses Carbonat 5 % bis weniger als 55 % des Gewichtes des durch das Carbonat adsorbierten und/oder absorbierten Silikates darstellt, und das Verhältnis des Gewichtes an verbleibendem, mit dem Silikat assoziiertem Wasser/Silikat, ausgedrückt in Trockengewicht, höher oder gleich 33/100 und niedriger oder gleich 120/100, vorzugsweise höher oder gleich 36/100 beträgt und das verbleibende, mit dem Silikat assoziierte Wasser nicht mit dem anderen mineralischen Produkt kombiniert ist,
    - eine Schüttdichte in der Größenordnung von 0,4 bis 1,5 g/cm3, vorzugsweise in der Größenordnung von 0,5 bis 1,5 g/cm3 und ganz besonders bevorzugt in der Größenordnung von 0,75 bis 1 g/cm3,
    - einen mittleren Durchmesser in der Größenordnung von 0,4 bis 1,8 mm, vorzugsweise in der Größenordnung von 0,5 bis 0,8 mm mit einer Abweichung Typ log10 von 0,02 bis 0,5, vorzugsweise von 0,05 bis 0,3.
EP93400359A 1992-03-20 1993-02-12 Builder auf Basis von Silikat und anorganischer Verbindung Revoked EP0561656B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR929203350A FR2688798B1 (fr) 1992-03-20 1992-03-20 Agent "builder" a base de silicate et d'un produit mineral.
FR9203350 1992-03-20

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EP0561656A1 EP0561656A1 (de) 1993-09-22
EP0561656B1 true EP0561656B1 (de) 1997-07-23

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US7867963B2 (en) 2007-06-12 2011-01-11 Rhodia Inc. Mono-, di- and polyol phosphate esters in personal care formulations
US7919449B2 (en) 2007-06-12 2011-04-05 Rhodia Operations Detergent composition with hydrophilizing soil-release agent and methods for using same
US7919073B2 (en) 2007-06-12 2011-04-05 Rhodia Operations Mono-, di- and polyol alkoxylate phosphate esters in oral care formulations and methods for using same
US8293699B2 (en) 2007-06-12 2012-10-23 Rhodia Operations Hard surface cleaning composition with hydrophilizing agent and method for cleaning hard surfaces
US8993506B2 (en) 2006-06-12 2015-03-31 Rhodia Operations Hydrophilized substrate and method for hydrophilizing a hydrophobic surface of a substrate

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DE4400024A1 (de) * 1994-01-03 1995-07-06 Henkel Kgaa Silikatische Builder und ihre Verwendung in Wasch- und Reinigungsmitteln sowie Mehrstoffgemische für den Einsatz auf diesem Sachgebiet
DE19504284A1 (de) * 1994-02-15 1995-08-17 Degussa Homogene Mischungen aus Alkalisilikat und Alkalikarbonat
DE4405511A1 (de) * 1994-02-22 1995-08-24 Henkel Kgaa Waschmittel mit amorphen silikatischen Buildersubstanzen
DE4406592A1 (de) * 1994-03-01 1995-09-07 Henkel Kgaa Verbesserte Mehrstoffgemische auf Basis wasserlöslicher Alkalisilikatverbindungen und ihre Verwendung, insbesondere zum Einsatz als Builder in Wasch- und Reinigungsmitteln
DE4415362A1 (de) * 1994-05-02 1995-11-09 Henkel Kgaa Verfahren zur Herstellung silikatischer Buildergranulate mit erhöhtem Schüttgewicht
FR2720074B1 (fr) * 1994-05-20 1996-08-09 Rhone Poulenc Chimie Composition détergente en poudre à base de percarbonate stabilisée par ajout de cogranulés silicate/carbonate.
DE19501269A1 (de) 1995-01-18 1996-07-25 Henkel Kgaa Amorphes Alkalisilikat-Compound
FR2732033B1 (fr) * 1995-03-20 1997-04-30 Rhone Poulenc Chimie Composition d'adjuvant de detergence diminuant les incrustations calciques, son utilisation dans des compositions detergentes et ces compositions detergentes
FR2732032B1 (fr) * 1995-03-20 1997-06-13 Rhone Poulenc Chimie Composition d'adjuvant de detergence diminuant les incrustations calciques, son utilisation dans des compositions detergentes et ces compositions detergentes
FR2735787B1 (fr) * 1995-06-26 1997-07-18 Rhone Poulenc Chimie Utilisation de cogranules de carbonate et de silicate de metal alcalin, comme agents alcalins reducteurs de la corrosion visible du verre et des decors dans les compositions detergentes
DE19525378A1 (de) * 1995-07-12 1997-01-16 Henkel Kgaa Amorphes Alkalisilicat-Compound
DE19533790A1 (de) * 1995-09-13 1997-03-20 Henkel Kgaa Verfahren zur Herstellung eines amorphen Alkalisilikats mit Imprägnierung
GB9609699D0 (en) * 1996-05-09 1996-07-10 Unilever Plc Detergent compositions
FR2751341B1 (fr) * 1996-07-16 2003-06-13 Rhone Poulenc Chimie Composition detergente pour lave-vaisselle, son utilisation en lave-vaisselle contre la corrosion de la vaisselle et procede de lavage non-corrosif de la vaisselle
FR2751340B1 (fr) * 1996-07-16 2003-06-13 Rhone Poulenc Chimie Composition detergente pour lave-vaisselle, son utilisation en lave-vaisselle contre la corrosion de la vaisselle et procede de levage non-corrosif de la vaisselle
JP4185188B2 (ja) 1998-07-17 2008-11-26 花王株式会社 複合粉体
CA2338822A1 (en) 1998-08-17 2000-02-24 The Procter & Gamble Company Multifunctional detergent materials
DE19858887A1 (de) * 1998-12-19 2000-06-21 Henkel Kgaa Kompaktat mit silicatischem Builder
GB0111043D0 (en) * 2001-05-08 2001-06-27 Ineos Silicas Ltd Granular compositions
FR2851572B1 (fr) 2003-02-20 2007-04-06 Rhodia Chimie Sa Composition nettoyante ou rincante pour surfaces dures
JP4761703B2 (ja) * 2003-04-02 2011-08-31 花王株式会社 シリカ分散液
FR2894585B1 (fr) 2005-12-14 2012-04-27 Rhodia Recherches Et Tech Copolymere comprenant des unites zwitterioniques et d'autres unites, composition comprenant le copolymere, et utilisation
US9096817B2 (en) 2007-11-06 2015-08-04 Rhodia Operations Copolymer for processing or modifying surfaces
FR2935390B1 (fr) 2008-08-26 2012-07-06 Rhodia Operations Copolymere pour le traitement ou la modification de surfaces

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GB136841A (de) * 1918-03-23 1900-01-01
US2909490A (en) * 1954-07-28 1959-10-20 Olin Mathieson Manufacture of duplex composition of sodium tripolyphosphate and sodium silicate solution
GB1396215A (en) * 1972-05-03 1975-06-04 Diamond Shamrock Corp Particulate detergent builders
US3895995A (en) * 1971-01-18 1975-07-22 Philadelphia Quartz Co Film drying of hydrated alkali metal silicate solutions
US4427417A (en) * 1982-01-20 1984-01-24 The Korex Company Process for preparing detergent compositions containing hydrated inorganic salts

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US3886079A (en) * 1971-09-27 1975-05-27 Burke Oliver W Jun Detergent compositions and detergent adjuvant combinations thereof, and processes for forming the same
JPS59157198A (ja) * 1983-02-28 1984-09-06 ライオン株式会社 嵩密度の小さい洗剤ビルダ−造粒物の製造法
FR2658497B1 (fr) * 1990-02-16 1992-05-15 Rhone Poulenc Chimie Granules de silicates hydrates de metaux alcalins, leur procede de preparation et leur application dans les compositions detergentes.
ES2083547T3 (es) * 1990-11-30 1996-04-16 Rhone Poulenc Chimie Agente mejorador de la detergencia, a base de silicatos de metales alcalinos, para composiciones detergentes.

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GB136841A (de) * 1918-03-23 1900-01-01
US2909490A (en) * 1954-07-28 1959-10-20 Olin Mathieson Manufacture of duplex composition of sodium tripolyphosphate and sodium silicate solution
US3895995A (en) * 1971-01-18 1975-07-22 Philadelphia Quartz Co Film drying of hydrated alkali metal silicate solutions
GB1396215A (en) * 1972-05-03 1975-06-04 Diamond Shamrock Corp Particulate detergent builders
US4427417A (en) * 1982-01-20 1984-01-24 The Korex Company Process for preparing detergent compositions containing hydrated inorganic salts
US4427417B1 (de) * 1982-01-20 1985-04-16

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8993506B2 (en) 2006-06-12 2015-03-31 Rhodia Operations Hydrophilized substrate and method for hydrophilizing a hydrophobic surface of a substrate
US7867963B2 (en) 2007-06-12 2011-01-11 Rhodia Inc. Mono-, di- and polyol phosphate esters in personal care formulations
US7919449B2 (en) 2007-06-12 2011-04-05 Rhodia Operations Detergent composition with hydrophilizing soil-release agent and methods for using same
US7919073B2 (en) 2007-06-12 2011-04-05 Rhodia Operations Mono-, di- and polyol alkoxylate phosphate esters in oral care formulations and methods for using same
US8268765B2 (en) 2007-06-12 2012-09-18 Rhodia Operations Mono-, di- and polyol phosphate esters in personal care formulations
US8293699B2 (en) 2007-06-12 2012-10-23 Rhodia Operations Hard surface cleaning composition with hydrophilizing agent and method for cleaning hard surfaces

Also Published As

Publication number Publication date
CN1079250A (zh) 1993-12-08
RO110261B1 (ro) 1995-11-30
CA2092060A1 (fr) 1993-09-21
BG97549A (bg) 1994-03-24
ATE155807T1 (de) 1997-08-15
FI931220A (fi) 1993-09-21
NO930984D0 (no) 1993-03-18
DE561656T1 (de) 1994-02-24
JP2745400B2 (ja) 1998-04-28
CZ43093A3 (en) 1993-12-15
DE69312357T2 (de) 1997-12-18
HU213318B (en) 1997-05-28
KR930019807A (ko) 1993-10-19
BG60918B1 (bg) 1996-06-28
HUT66732A (en) 1994-12-28
FR2688798A1 (fr) 1993-09-24
FR2688798B1 (fr) 1994-10-14
EE9400090A (et) 1995-12-15
NO930984L (no) 1993-09-21
HU9300798D0 (en) 1993-07-28
JPH06184593A (ja) 1994-07-05
PL172893B1 (pl) 1997-12-31
SK19793A3 (en) 1993-12-08
FI931220A0 (fi) 1993-03-19
DK0561656T3 (da) 1997-08-25
PL298126A1 (en) 1993-12-27
RU2103340C1 (ru) 1998-01-27
PL173265B1 (pl) 1998-02-27
GR3024804T3 (en) 1998-01-30
YU18393A (sh) 1996-05-20
BR9301207A (pt) 1993-09-28
DE69312357D1 (de) 1997-08-28
JPH09194209A (ja) 1997-07-29
JP2533053B2 (ja) 1996-09-11
EP0561656A1 (de) 1993-09-22
ES2105146T3 (es) 1997-10-16

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