Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—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 Q 2 and Q 3 form , intended for detergent compositions, in particular for powdered detergents, in particular for washing machine or 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, it must be checked to avoid encrustations on the laundry or parts 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 must also provide 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 less used in phosphate-free compositions for washing machines.
• the silicates most used in this application are those having a SiO 2 / Na 2 0 molar ratio of between 1.6 and 2.4. They are marketed 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 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 quine powder silicate contains only 20 to 22% by weight of associated water (relative to the product finished), 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.
• the Applicant has found that when an alkali metal silicate is rich in species in which the silicon atoms are in Q 2 and Q 3 form , the polyanionic species formed by dilution up to 1 to 3 g / l in a washing medium have a sufficient lifespan to allow them to play a role of "builder" in detergency.
• silicon atoms in Q 2 and Q3 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;
• Q3 means that each silicon atom participates in three -Si-O-Si- bonds, the remaining bond being a -Si-OX termination.
• the "builder” agent for detergent composition which is the subject of the invention, is characterized in that it consists of an alkali metal silicate, in particular of sodium or potassium, containing at least 30%, preferably at least 50% of silicon atoms in Q 2 and Q 3 form .
• Said silicate can have a SiO 2 / M 2 0 molar ratio of the order of 1.6 to 3.5, preferably of the order of 1.8 to 2.6.
• Said builder agent can be in any form, structured (powder, granules, etc.) or not.
• a first embodiment of the invention is a "builder" agent consisting of an aqueous solution of about 10-60%, preferably about 35-50% by weight of dry extract of an alkali metal silicate, in particular of sodium or potassium, Si0 2 / M 2 0 molar ratio of the order of 1.6 to 3.5, preferably of the order of 1.8 to 2.6.
• 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 adsorbing power of the powders.
• the powder 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 nonlimiting 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 Si0 2 / M 2 0 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 an inert particulate support vis- with respect to the silicate, the silicate weight ratio expressed in 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.
• inorganic supports of the silicate solution or may mention preferably water-soluble compounds such as: sodium carbonate, sodium sulfate, sodium borate, sodium perborate, sodium metasilicate, phosphates or polyphosphates such as trisodium phosphate, sodium tripolyphosphate, etc., these supports being present alone or as a mixture between them.
• water-soluble compounds such as: sodium carbonate, sodium sulfate, sodium borate, sodium perborate, sodium metasilicate, phosphates or polyphosphates such as trisodium phosphate, sodium tripolyphosphate, etc.
• 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).
• Said supported solution can be prepared by adsorption and / or absorption by contacting a concentrated aqueous solution of an alkali metal silicate with a molar ratio Si0 2 / M 2 0 of the order of 1.6 to 3.5 , preferably of the order of 1.8 to 2.6, and having a dry extract of the order of 10 to 60%, preferably of the order of 35 to 50%, with an inert inorganic support vis- with respect to silicate, said support 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 as dry / water associated with silicate of the order of 100 / 120 to 100/40, preferably of the order of 100/90 to 100/50.
• 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 list above.
• 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 rate of water not associated with the silicate which may be in the form 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 / M20 molar ratio of the order of 1.6 to 3.5, preferably of the order of 1.8 to 2.6 and very 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 that of carbonate particles.
• anti-deposition polymers carboxymethyl - cellulose
• enzymes ... commonly used in the detergency domain, having a diameter and a density close to that 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 co-granules consists in using a rotary granulator allowing the particles to travel in a thin layer.
• Drageeners 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 the order of 15 to 200 ° C, preferably of on the order of 15 to 120 ° C and especially 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 1 / kg, preferably from 0.4 to 0.7 I / kg and very particularly from 0.62 to 0.7 1 / 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 room 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 staircase 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 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).
• the detergent composition there is present in the detergent composition at least one surfactant 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 lasts 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 stainless steel pots of 2 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 / I (mass counted as dry matter of product) and 2 g / I of LABS are added thereto.
• test pieces are wrung out, they are 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 about 110 ° C.
• the GARDNER device is calibrated by measuring zero on a black plate reserved for this purpose then by reading values L, a, b on a standardized white plate of the same type as the black one.
• 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 tripolyphosphate H 2 @ sold by Rhône-Poulenc.
• the average residence time of a particle in the plate is approximately 10 to 15 minutes.
• the temperature of the particles leaving the plate is room temperature.
• the plate outlet granules are introduced into a smooth-walled rotating tube with a diameter of 500 mm, a length of 1300mm 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 thus obtained are dried in a fluidized bed at a temperature of the order of 80 ° C (temperature of the fluidizing air equal to 85 ° -90 ° C) for 10 to 15 minutes.
• the granules exhibit excellent storage behavior.
• drum rotation speed 10 rpm
• 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 outlet 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.
• the cogranules leaving 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.
• This product is introduced by dry mixing with additives in order to obtain the following composition for washing machine:
• the soil removal performance test is carried out in a WAS-CATOR 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 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% of 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 ° French TH.
• the plates are then subjected to a photometric measurement using a GARDNER device, identical to that used in Examples 1 to 5.
• the total quantity of light L returned by the sample is measured.

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• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (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)
• Detergent Compositions (AREA)
• Glanulating (AREA)
• Adornments (AREA)
• Ceramic Products (AREA)
• Silicates, Zeolites, And Molecular Sieves (AREA)

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• 1991
  • 1991-11-25 DE DE91403173T patent/DE488868T1/de active Pending
  • 1991-11-25 EP EP91403173A patent/EP0488868B1/de not_active Revoked
  • 1991-11-25 DE DE69117270T patent/DE69117270T2/de not_active Revoked
  • 1991-11-25 AT AT91403173T patent/ATE134381T1/de not_active IP Right Cessation
  • 1991-11-25 ES ES91403173T patent/ES2083547T3/es not_active Expired - Lifetime
  • 1991-11-25 DK DK91403173.7T patent/DK0488868T3/da active
  • 1991-11-28 NO NO914675A patent/NO300898B1/no unknown
  • 1991-11-29 FI FI915657A patent/FI915657A7/fi unknown
  • 1991-11-29 CA CA002056674A patent/CA2056674C/fr not_active Expired - Lifetime
  • 1991-11-29 JP JP3339478A patent/JP2631051B2/ja not_active Expired - Lifetime
  • 1991-11-30 KR KR1019910021898A patent/KR950010008B1/ko not_active Expired - Fee Related
• 1995
  • 1995-10-03 JP JP7278233A patent/JP2594893B2/ja not_active Expired - Lifetime
• 1996
  • 1996-03-20 GR GR960400775T patent/GR3019375T3/el unknown
  • 1996-09-30 LV LVP-96-390A patent/LV11744B/lv unknown

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