EP0488868B1 - Gerüststoff auf Basis von Alkalimetallsilikaten für Reinigungsmittelzusammensetzungen - Google Patents

Gerüststoff auf Basis von Alkalimetallsilikaten für Reinigungsmittelzusammensetzungen Download PDF

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Publication number
EP0488868B1
EP0488868B1 EP91403173A EP91403173A EP0488868B1 EP 0488868 B1 EP0488868 B1 EP 0488868B1 EP 91403173 A EP91403173 A EP 91403173A EP 91403173 A EP91403173 A EP 91403173A EP 0488868 B1 EP0488868 B1 EP 0488868B1
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EP
European Patent Office
Prior art keywords
silicate
order
alkali metal
weight
process according
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EP91403173A
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English (en)
French (fr)
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EP0488868A2 (de
EP0488868A3 (de
Inventor
Patrick Boittiaux
Daniel Joubert
Jean-Claude Lotiss. Le Grand Caillouet Kiefer
Jérome Le Roux
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Rhodia Chimie SAS
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Rhone Poulenc Chimie SA
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Priority claimed from FR9014999A external-priority patent/FR2669838B1/fr
Priority claimed from FR9107710A external-priority patent/FR2677994B1/fr
Application filed by Rhone Poulenc Chimie SA filed Critical 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
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C11D7/14—Silicates

Definitions

  • the subject of the present invention is a "builder" agent consisting of alkali metal silicates rich in species in which the silicon atoms are in Q2 and Q3 form, intended for detergent compositions, in particular for powdered detergents, in particular for washing machines or for dishwasher.
  • 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, this must be checked to avoid encrustation on the laundry or 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 considered good detergency builders, particularly in combination with tripolyphosphates as in US-A-2,909,490, but they are currently used less in phosphate-free compositions for washing machines.
  • Detergent formulations comprising silicate with an SiO2 / Na2O ratio of between 0.9 and 1.6, and more preferably of the order of 1, sodium carbonate, tripolyphosphate and copolymers of acrylic and maleic acid have been proposed in patent EP-A-353,562.
  • silicates in the detergency application are those having a SiO2 / Na2O molar ratio of between 1.6 and 2.4. They are sold either in the form of concentrated solutions containing approximately 35-45% by weight of dry extract, or in the form of powdered silicate, atomized and optionally compacted.
  • 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 20 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.
  • Such 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 DE-A-2 322 123 describes the preparation of silicate carbonate particles consisting in bringing a silicate solution into contact with carbonate particles, then in drying the mixture so as to remove the water vapor from the silicate.
  • Patent FR-A-2 143 093 describes the co-drying by atomization of a silicate solution mixed with an additive such as in particular sodium carbonate. This co-drying is carried out at a temperature between 300 and 450 ° C. so that the water contained in the silicate vaporizes and escapes.
  • US-A-4,761,248 also describes a process for the preparation of hydrated particles from a hydratable anhydrous compound and a silicate solution, the water of the latter ensuring the hydration of the hydratable compound.
  • US-A-4,427,417 describes the mixture of agglomerates of hydratable detergent particles and a silicate solution, the water of the latter serving to hydrate the hydratable compounds, followed by drying.
  • the Applicant has found that when an alkali metal silicate is rich in species in which the silicon atoms are in Q2 and Q3 form, the polyanionic species formed by dilution up to 1 to 3 g / l in a washing medium have a duration of sufficient life to allow them to play a role of "builder" in detergency.
  • silicon atoms in Q2 and Q3 form is a representation of the degree of association of the silicon atoms with each other;
  • Q2 means that each silicon atom participates in two -Si-O-Si- bonds, the two remaining bonds being a -Si-OX termination where X is an alkali metal or H;
  • Q3 means that each silicon atom participates in three -Si-O-Si- bonds, the remaining bond being a -Si-OX termination.
  • a first object of the invention consists in the use as a builder agent in a detergent composition of an aqueous solution of alkali metal silicate, in particular of sodium or potassium, at approximately 10 to 60% by weight.
  • dry extract preferably about 35 to 50%
  • the concentrated solution of alkali metal silicate used as “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.
  • Said "builder” solution can be used in post addition by spraying on the "bottom of tower” washing powder in the case of an atomization installation or on the mixture of the components of the washing formula in the case of a mixing with dry, and within the limit of the adsorption capacity of the powders.
  • the pulverulent mixture obtained can be dried moderately if necessary, so that the dry silicate / water weight ratio remaining associated with the silicate is between 100/120 and 100/40, preferably between 100/90 and 100/50.
  • the quantity of silicate solution that can be used is such that the dry silicate / detergent powder weight ratio is between 1/100 and 30/100, preferably of the order of 10/100 to 20/100.
  • Another non-limiting embodiment of the invention consists of an aqueous solution of about 10-60%, preferably about 35-50% by weight of dry extract of an alkali metal silicate, especially sodium or potassium. , of SiO2 / M2O molar ratio of the order of 1.6 to 3.5, preferably of the order of 1.8 to 2.6, adsorbed and / or absorbed on a particulate support inert with respect to silicate, the silicate weight ratio expressed as dry / water remaining associated with the silicate ranging from 100/120 to 100/40, preferably ranging from 100/90 to 100/50.
  • “Inert” means chemically inert.
  • water associated with the silicate is understood to mean the water of the supported solution which is not combined with the mineral support, in particular in the form of crystallized hydrate.
  • a second object of the invention consists of a "builder" agent, characterized in that it is capable of being obtained by adsorption and / or absorption by bringing into contact a concentrated aqueous solution of an alkali metal silicate of SiO2 / M2O ratio of the order of 1.6 to 3.5, preferably of the order of 1.8 to 2.6, and having a solids content of the order of 10 to 60%, preferably of on the order of 35 to 50%, containing at least 30% of silicon atoms, preferably at least 50%, with an inert inorganic support with respect to the silicate, said support being different from sodium tripolyphosphate and being present in an amount such that the amount of water remaining associated with said silicate after adsorption and / or absorption corresponds to a silicate weight ratio expressed in dry / water associated with the silicate of the order of 100/120 to 100/40, preferably from 100/90 to 100/50.
  • organic supports of the silicate solution mention may be made of preferably water-soluble compounds such as: sodium carbonate, sodium sulfate, sodium borate, sodium perborate, sodium metasilicate, phosphates such as trisodium phosphate, ..., these supports being present alone or as a mixture between them.
  • the support generally represents of the order of 55 to 95%, preferably of the order of 65 to 85% of the weight of the supported solution expressed in dry (i.e. weight of solution expressed in dry + weight support).
  • the contacting operation can be carried out by adding, in particular by spraying, said concentrated silicate solution to the support in particulate form, in any known mixer with high shear, in particular of the LODIGE® type, or in the granulation tools ( drum, plate ...) ..., at a temperature of around 20 to 95 ° C, preferably around 70 to 95 ° C.
  • the supports that can be used are those already mentioned in the above list.
  • the quantity and the concentration of the silicate solution to be used depend on the absorbing and / or adsorbing power of the support, taking into account a possible possibility for said support 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 defined hydrates can be determined by appropriate physicochemical methods (thermoporosimetry, thermogravimetry, proton NMR, IR).
  • the limit of absorbent and / or adsorbent capacity of said support can be determined according to known methods, for example by measuring the evolution of the angle at the base of the slope of slope as a function of the rate of addition of the solution of silicate.
  • the mixture consisting of the support and the silicate solution can itself be dried, but in a moderate manner so as to obtain the desired proportions of water associated with the silicate.
  • the particles of supported silicate solution obtained can be ground, if desired, so as to obtain an average diameter of the order of 200 to 800 micrometers.
  • Solutions of alkali metal silicate in the form adsorbed and / or absorbed on an alkali metal carbonate and being in the form of spherical cogranules of hydrated alkali metal silicate and alkali metal carbonate are builder agents of the invention particularly efficient.
  • alkali metal silicates and carbonates mention may preferably be made of those of sodium and potassium, and very particularly those of sodium.
  • the aqueous solution based on silicate or on a sprayed silicate / carbonate mixture may have a dry extract content of the order of 30 to 55% by weight, preferably 30 to 45% by weight; said alkali metal silicate has a SiO2 / M2O molar ratio of the order of 1.6 to 3.5, preferably of the order of 1.8 to 2.6 and all particularly close to 2; said carbonate may optionally be present in proportions depending on the desired final product.
  • the spraying of the silicate-based solution or of a 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.
  • carbonate particles may be present small amounts (less than 10% of the weight of the cogranules) of other particles, such as anti-deposition polymers (carboxymethyl - cellulose ...), enzymes ... commonly used in the detergency domain, having a diameter and a density close to those of carbonate particles.
  • anti-deposition polymers carboxymethyl - cellulose
  • enzymes ... commonly used in the detergency domain, having a diameter and a density close to those of carbonate particles.
  • the device used to carry out the co-granulation operation by spraying can be any rotary device of the rotating plate, bezel, rotating drum, mixer-granulator type, etc.
  • 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 carbonate-based particles pass at a temperature of on the order of 15 to 200 ° C, preferably on the order of 15 to 120 ° C and most particularly on the order of 15 to 30 ° C.
  • the quantities of silicate-based solution or of silicate / carbonate mixture to be sprayed and of carbonate-based particles to be used correspond to a liquid flow rate / particle flow rate which can range from 0.2 to 0.8 l / kg, preferably from 0.4 to 0.7 l / kg and very particularly from 0.62 to 0.7 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 the cogranules obtained in the granulation step in a rotary device.
  • This device is preferably 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 also 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 densified cogranules are then 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; the skilled person knows how to adapt these different conditions to the product sought.
  • dissolution rate at 90% or 95% in water means the time necessary to dissolve 90% or 95% of the 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 at a rate 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 relative to by weight of composition).
  • 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 simplified machine washing is simulated in a tergotometer, by washing standardized soiled tissue test tubes at 65 ° C. with a surfactant and the builder to be tested. Washing takes twenty minutes and the color of the fabrics is measured before and after washing. We make a "blank", by washing the same type of test tubes with the surfactant alone, to evaluate the performance of the builder tested.
  • the tergotometer is a device made up of 4 2-liter stainless steel pots on which are fitted pulsators which are set at 100 cycles per minute. The pots are placed in a water tank regulated at 65 ° C.
  • the builder is tested at 4 g / l (mass counted as dry matter of product) and 2 g / l of LABS are added thereto.
  • the specimens are wrung out and pre-dried by spreading them individually in absorbent paper.
  • the fabrics are then passed twice in a freezer between two sheets of absorbent paper at a temperature of approximately 110 ° C.
  • the average DL and DE is calculated for each product and each type of soiled tissue.
  • a LODIGE M5G® mixer (sold by LODIGE) is loaded with 800 g of anhydrous H2® tripolyphosphate sold by Rhône-Poulenc.
  • the average residence time of a particle in the plate is approximately 10 to 15 min.
  • the temperature of the particles leaving the plate is ambient temperature.
  • the plate outlet granules are introduced into a smooth-walled rotating tube with a diameter of 500 mm, a length of 1300 mm and having an inclination of the order of 5%.
  • the outlet diaphragm is adjusted so that the average residence time of a particle is approximately 40 min.
  • the speed of rotation of the drum (18 rpm) is chosen so as to have a rolling bed of particles, which promotes densification of the latter.
  • the granules exhibit excellent storage behavior.
  • the granules exhibit excellent storage behavior.
  • the granulation system consists of a drum rotating at 40 rpm, with smooth walls of diameter 500 mm, length 1300 mm and having an inclination of the order of 7.5%.
  • the output diaphragm is adjusted so that the average residence time of a particle is of the order of 15 to 20 min.
  • the drum is continuously fed at a flow rate of 37 kg / h by a carbonate powder having the same characteristics as those of the powder of Examples 1 and 2.
  • a silicate solution (having an active material content of 45.6% by weight and a SiO2 / Na2O weight ratio of 2) at 80 ° C. with a flow rate of 18 l / h.
  • 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.
  • the granules exhibit excellent storage behavior.
  • the granules exhibit excellent storage behavior.
  • the dirt removal performance test is carried out in a WASCATOR FOM 71 ® 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 reflectances are determined using the blue trichromatic component, without the action of optical brighteners.
  • Number of measurements per sample 4
  • Number of samples per wash 2
  • Number of washes 3
  • X 2 X 3 24 measurements by soiling, by product and by concentration studied.
  • 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.
  • Example 8 The product of Example 8 is introduced by mixing into a LODIGE M5G® with additives in order to obtain compositions for dishwashers.
  • compositions are tested in a MIELE® household dishwasher whose water softener is not regenerated; therefore it delivers hard water with a total hardness of 30 ° TH French.
  • the plates are then subjected to a photometric measurement using a GARDNER® device, identical to that used in Examples 1 to 5.
  • the total amount of light L returned by the sample is measured.

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

Claims (27)

  1. Verwendung als Builder bzw. Gerüststoff in einer Reinigungsmittelzusammensetzung, einer wäßrigen Alkalimetallsilikatlösung, insbesondere Natrium- oder Kaliumsilikatlösung, mit etwa 10 bis etwa 60 Gew.-% Trockenextrakt und einem Molverhältnis SiO₂/M₂O in der Größenordnung von 1,6 bis 3,5, enthaltend mindestens 30 % Siliziumatome in Form von Q₂ und Q₃, wobei die Form Q₂ bedeutet, daß jedes Siliziumatom an zwei Bindungen -Si-O-Si- teilnimmt, und die zwei restlichen Bindungen eine Endung -Si-O-X sind, wobei X ein Alkalimetall oder Wasserstoff ist, und die Form Q₃ bedeutet, daß jedes Siliziumatom an drei Bindungen -Si-O-Si- teilnimmt, wobei die restliche Bindung eine Endung -Si-O-X ist.
  2. Verwendung gemäß Anspruch 1, dadurch gekennzeichnet, daß die Alkalimetall-, insbesondere Natrium- oder Kaliumsilikatlösung, mindestens 50 % Siliziumatome in Form von Q₂ und Q₃ enthält.
  3. Verfahren zur Herstellung eines Builders bzw. Gerüststoffs, dadurch gekennzeichnet, daß man adsorbiert und/oder absorbiert durch Inkontaktbringen einer konzentrierten, wäßrigen Lösung eines Alkalimetalls mit dem Molverhältnis SiO₂/M₂O in der Größenordnung von 1,6 bis 3,5, welche einen Trockenextrakt in der Größenordnung von 10 bis 60 % aufweist, und mindestens 30 % Siliziumatome in Form von Q₂ und Q₃ enthält, mit einem gegenüber Silikat inerten, anorganischen Träger, wobei dieser Träger verschieden ist von Natriumtripolyphosphat und in einer solchen Menge vorliegt, daß die Restwassermenge, die mit diesem Silikat nach Adsorption und/oder Absorption assoziiert ist, einem Silikatgewichtsverhältnis ausgedrückt als Trockensubstanz/Wasser, das mit dem Silikat assoziiert ist, in der Größenordnung von 100/120 bis 100/40 entspricht, wobei die Form Q₂ bedeutet, daß jedes Siliziumatom an zwei Bindungen -Si-O-Si- teilnimmt, wobei die zwei restlichen Bindungen eine Endung -Si-O-X bedeuten, wobei X ein Alkalimetall oder H ist, und die Form Q₃ bedeutet, daß jedes Siliziumatom an drei Bindungen -Si-O-Si- teilnimmt, wobei die restliche Bindung eine Endung -Si-O-X ist.
  4. Verfahren gemäß dem vorhergehenden Anspruch, dadurch gekennzeichnet, daß der Träger ausgewählt ist unter Natriumcarbonat, Natriumsulfat, Natriumborat, Natriumperborat, Natriummetasilikat, einem Phosphat wie Trinatriumphosphat, allein oder im Gemisch.
  5. Verfahren gemäß dem vorhergehenden Anspruch, dadurch gekennzeichnet, daß der genannte Träger Natriumcarbonat ist.
  6. Verfahren gemäß einem der Ansprüche 3 bis 5 , dadurch gekennzeichnet, daß der Arbeitsgang des Inkontaktbringens durch Zerstäubung der genannten konzentrierten Silikatlösung auf dem Träger in Teilchenform bei einer Temperatur im Bereich von 20 °C bis 95 °C erfolgt.
  7. Verfahren zur Herstellung von kugeligen Cogranulaten von hydratisierten Alkalimetallsilikaten und Alkalimetallcarbonaten, dadurch gekennzeichnet, daß man:
    - eine wäßrige Lösung auf Basis von Alkalimetallsilikaten, enthaltend mindestens 30 % Siliziumatome in Form Q₂ und Q₃, oder auf Basis einer Mischung dieser Silikate und von Alkalimetallcarbonaten auf einem Rollbett bzw. Wirbelbett von Teilchen auf Basis von Alkalimetallcarbonaten, das in einem Granulationsrotationsvorrichtung vorbeiläuft, zerstäubt, wobei die Ablaufgeschwindigkeit der Teilchen, die Dicke des Rollbettes und der Verbrauch der zerstäubten Lösung derart sind, daß jedes Teilchen sich in ein plastisches Cogranulat umwandelt, indem es mit anderen Teilchen in Kontakt tritt,
    - die erhaltenen Cogranulate einem Verdichtungsvorgang unterwirft,
    - die verdichteten Cogranulate trocknet, bis man einen Gehalt an dem Silikat assoziierten Wasser erhält, der einem Gewichtsverhältnis Silikat, ausgedrückt in Trockensubstanz/an das Silikat assoziiertes Wasser in der Größenordnung von 100/120 bis 100/40 erhält,
    wobei die Form Q₂ bedeutet, daß jedes Siliziumatom an zwei Bindungen -Si-O-Si- teilnimmt, wobei die beiden restlichen Bindungen eine Endung -Si-O-X sind, wobei X ein Alkalimetall oder H bedeutet; und die Form Q₃ bedeutet, daß jedes Siliziumatom an drei Bindungen -Si-O-Si- teilnimmt, und die restliche Bindung eine Endung -Si-O-X ist.
  8. Verfahren gemäß Anspruch 7, dadurch gekennzeichnet, daß die zerstäubte, wäßrige Lösung auf Silikatbasis oder einer Mischung Silikat/Carbonat einen Wert an Trockenextrakt in der Größenordnung von 30 bis 55 Gew.-% aufweist, wobei das genannte Alkalimetallsilikat ein Molverhältnis SiO₂/M₂O in der Größenordnung von 1,6 bis 3,5 aufweist, wobei das genannte Carbonat gegebenenfalls gemäß Verhältnissen, die eine Funktion des gewünschten endgültigen Produktes sind, vorliegt.
  9. Verfahren gemäß Anspruch 7 oder 8, dadurch gekennzeichnet, daß die Zerstäubung der Lösung auf Silikatbasis und/oder der Mischung Silikat/Carbonat bei einer Temperatur im Bereich von 20 °C bis 95 °C durchgeführt wird.
  10. Verfahren gemäß einem der Ansprüche 7 bis 9 , dadurch gekennzeichnet, daß die das Rollbett bzw.Wirbelbett bildenden Teilchen auf Basis eines Alkalimetallcarbonats sind, aufweisend:
    - einen mittleren Durchmesser in der Größenordnung von 10 bis 150 10⁻⁶ m,
    - eine nicht gepreßte Füll- bzw. Schüttdichte in der Größenordnung von 0,4 bis 1,1 g/cm³,
    - einen Wassergehalt in der Größenordnung von 0,05 bis 0,4 %,
    - einen Gehalt an unlöslichen Stoffen in der Größenordnung von 5 bis 100 mg/kg.
  11. Verfahren gemäß einem der Ansprüche 7 bis 10, dadurch gekennzeichnet, daß die Teilchen, welche das Rollbett bilden, weniger als 10 % des Gewichtes der Cogranulate an Teilchen von anderer Natur als Alkalimetallcarbonat enthalten, und einen Durchmesser und eine Dichte etwa derjenigen der Alkalimetallcarbonatteilchen aufweisen.
  12. Verfahren gemäß einem der Ansprüche 7 bis 11, dadurch gekennzeichnet, daß die Granulationsvorrichtung ein Rotationsgranulator ist, welcher den Ablauf der Teilchen in dünner Schicht erlaubt.
  13. Verfahren gemäß Anspruch 12 , dadurch gekennzeichnet, daß der Rotationsgranulator eine Dragierapparatur ist.
  14. Verfahren gemäß einem der Ansprüche 7 bis 11, dadurch gekennzeichnet, daß die Granulationsvorrichtung eine Trommel ist.
  15. Verfahren gemäß einem der Ansprüche 7 bis 14 , dadurch gekennzeichnet, daß die Teilchen auf Basis von Carbonat bei einer Temperatur im Bereich von 15 °C bis 200 °C ablaufen.
  16. Verfahren gemäß einem der Ansprüche 7 bis 15 , dadurch gekennzeichnet, daß die zu zerstäubenden Mengen der Lösung auf Basis von Silikat oder Mischung Silikat/Carbonat und die einzusetzenden Teilchen auf Basis von Carbonat einem Verhältnis Flüssigkeitsverbrauch/Teilchenverbrauch entsprechen, das von 0,2 bis 0,8 l/kg gehen kann, wobei diese Werte als Natriumsalze ausgedrückt sind.
  17. Verfahren gemäß einem der Ansprüche 7 bis 16 , dadurch gekennzeichnet, daß der Verdichtungsvorgang bei Umgebungstemperatur durch Rollen bzw. Wälzen der in der Granulationsstufe erhaltenen Cogranulate in einer Rotationsvorrichtung durchgeführt wird.
  18. Verfahren gemäß Anspruch 17, dadurch gekennzeichnet, daß der Verdichtungsvorgang in einer Rotationstrommel durchgeführt wird.
  19. Verfahren gemäß einem der Ansprüche 7 bis 18 , dadurch gekennzeichnet, daß die nach der Verdichtung erhaltenen Cogranulate in fluidisiertem Bett getrocknet werden.
  20. Verfahren gemäß einem der Ansprüche 7 bis 19 , dadurch gekennzeichnet, daß den nach dem Trocknen erhaltenen Cogranulaten kleine Mengen flüssiger Verbindungen, die üblicherweise auf dem Reinigungsmittelgebiet verwendet werden, durch Zerstäubung zugesetzt werden.
  21. Verwendung von Cogranulaten, welche in der Lage sind, nach einem der Ansprüche 7 bis 20 erhalten zu werden, als Builder bzw. Gerüststoff entweder bei der Herstellung einer Reinigungsmittelzusammensetzung oder als wesentliches Element einer Reinigungsmittelzusammensetzung.
  22. Verwendung gemäß Anspruch 21, dadurch gekennzeichnet, daß die Reinigungsmittelzusammensetzung eine Pulverreinigungszusammensetzung für die Geschirrspülmaschine ist, mit einer Menge von 3 bis 90 Gew.-% Trockensilikat in bezug auf die Zusammensetzung.
  23. Verwendung gemäß Anspruch 21, dadurch gekennzeichnet, daß die Reinigungsmittelzusammensetzung eine Pulverreinigungszusammensetzung zum Wäschewaschen ist, mit einer Menge von 3 bis 60 Gew.-% Trockensilikat in bezug auf die Zusammensetzung,
EP91403173A 1990-11-30 1991-11-25 Gerüststoff auf Basis von Alkalimetallsilikaten für Reinigungsmittelzusammensetzungen Revoked EP0488868B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR9014999 1990-11-30
FR9014999A FR2669838B1 (fr) 1990-11-30 1990-11-30 Cogranules spheriques de silicates de metaux alcalins et de carbonates de metaux alcalins, leur procede de preparation et leur application dans les compositions detergentes.
FR9107710 1991-06-24
FR9107710A FR2677994B1 (fr) 1991-06-24 1991-06-24 Agent "builder" a base de silicates de metaux alcalins pour compositions detergentes.

Publications (3)

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EP0488868A2 EP0488868A2 (de) 1992-06-03
EP0488868A3 EP0488868A3 (de) 1992-06-17
EP0488868B1 true EP0488868B1 (de) 1996-02-21

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EP91403173A Revoked EP0488868B1 (de) 1990-11-30 1991-11-25 Gerüststoff auf Basis von Alkalimetallsilikaten für Reinigungsmittelzusammensetzungen

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EP (1) EP0488868B1 (de)
JP (2) JP2631051B2 (de)
KR (1) KR950010008B1 (de)
AT (1) ATE134381T1 (de)
CA (1) CA2056674C (de)
DE (2) DE69117270T2 (de)
DK (1) DK0488868T3 (de)
ES (1) ES2083547T3 (de)
FI (1) FI915657A (de)
GR (1) GR3019375T3 (de)
LV (1) LV11744B (de)
NO (1) NO300898B1 (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6013617A (en) * 1996-01-19 2000-01-11 Rhone-Poulenc Chimie Q2 /Q3 alkali metal silicate/inorganic compound detergent builders
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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US5427711A (en) * 1991-12-29 1995-06-27 Kao Corporation Synthesized inorganic ion exchange material and detergent composition containing the same
JP2525318B2 (ja) * 1991-12-29 1996-08-21 花王株式会社 合成無機ビルダ―
FR2688798B1 (fr) * 1992-03-20 1994-10-14 Rhobb Poulenc Chimie Agent "builder" a base de silicate et d'un produit mineral.
FR2708620B1 (fr) * 1993-08-06 1995-09-01 Rhone Poulenc Chimie Utilisation de siliconate dans des compositions détergentes pour le lavage automatique de la vaisselle.
US5744639A (en) * 1993-12-03 1998-04-28 Solutia Inc. Granular alkali metal nitrilotriacetate
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
GB9402301D0 (en) * 1994-02-07 1994-03-30 Brunner Mond & Co Ltd Granular builder product
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
US5618783A (en) * 1994-03-03 1997-04-08 Kao Corporation Synthesized inorganic ion exchange material and detergent composition containing the same
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
GB9504442D0 (en) * 1995-03-06 1995-04-26 Brunner Mond & Co Ltd Granular bleach/builder product
FR2732355B1 (fr) * 1995-03-29 1997-04-30 Rhone Poulenc Chimie Formulation detergente compacte en poudre pour lavage du linge
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
US5998663A (en) * 1998-01-14 1999-12-07 Solutia, Inc. Granular alkali metal nitrilotriacetate
US6541443B1 (en) 1998-08-17 2003-04-01 The Procter & Gamble Company Multifunctional detergent materials
US6594422B2 (en) 2001-05-02 2003-07-15 Motorola, Inc. Opto-coupling device structure and method therefor
FR2851572B1 (fr) 2003-02-20 2007-04-06 Rhodia Chimie Sa Composition nettoyante ou rincante pour surfaces dures
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
EP2212409B1 (de) 2007-11-06 2017-08-16 Rhodia Opérations Copolymer zur behandlung wäsche oder harter oberflächen
FR2935390B1 (fr) 2008-08-26 2012-07-06 Rhodia Operations Copolymere pour le traitement ou la modification de surfaces
FR2973034B1 (fr) 2011-03-21 2014-05-02 Ard Sa Nouvelles compositions d'oligomeres polyesters et utilisation comme agents tensioactifs

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NL297419A (de) * 1962-09-04
US4022704A (en) * 1971-06-21 1977-05-10 Stauffer Chemical Company Production of spray dried, high bulk density hydrous sodium silicate mixtures
US3821119A (en) * 1972-05-03 1974-06-28 Diamond Shamrock Corp Silicated soda ash
US4169806A (en) * 1978-08-09 1979-10-02 The Procter & Gamble Company Agglomeration process for making granular detergents
US4427417A (en) * 1982-01-20 1984-01-24 The Korex Company Process for preparing detergent compositions containing hydrated inorganic salts
US4761248A (en) * 1986-11-06 1988-08-02 Kerr-Mcgee Chemical Corporation Process for preparing particulate detergent products
DE3825858A1 (de) * 1988-07-29 1990-02-01 Henkel Kgaa Phosphatarme buildersalzkombination

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6013617A (en) * 1996-01-19 2000-01-11 Rhone-Poulenc Chimie Q2 /Q3 alkali metal silicate/inorganic compound detergent builders
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
FI915657A0 (fi) 1991-11-29
EP0488868A2 (de) 1992-06-03
CA2056674C (fr) 2002-03-19
DE69117270D1 (de) 1996-03-28
GR3019375T3 (en) 1996-06-30
JPH04275400A (ja) 1992-09-30
LV11744A (lv) 1997-04-20
DK0488868T3 (da) 1996-03-18
KR920009970A (ko) 1992-06-26
JPH08209190A (ja) 1996-08-13
JP2594893B2 (ja) 1997-03-26
CA2056674A1 (fr) 1992-05-31
JP2631051B2 (ja) 1997-07-16
ES2083547T3 (es) 1996-04-16
KR950010008B1 (ko) 1995-09-04
DE69117270T2 (de) 1996-11-14
NO300898B1 (no) 1997-08-11
ATE134381T1 (de) 1996-03-15
LV11744B (en) 1997-08-20
DE488868T1 (de) 1994-02-03
FI915657A (fi) 1992-05-31
NO914675D0 (no) 1991-11-28
NO914675L (no) 1992-06-01
EP0488868A3 (de) 1992-06-17

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