EP0488868A2 - Alcaline metal silicate based builder for detergent compositions - Google Patents

Abstract

Builder agent for powdered detergent composition, consisting of an alkali metal silicate rich in silicon atoms in the Q2 and Q3 form. A solution of alkali metal silicate with an SiO2/M2O ratio of 1.6 to 3.5 which, as such, has a solids content of 10 - 60 % or which is in supported form, especially in the form of cogranulates, the weight ratio of silicate expressed on dry basis/water associated with the silicate ranging from 100/120 to 100/40, is an example of a silicate rich in silicon atoms in the Q2 and Q3 form. Use in powdered detergent compositions, especially for a washing machine and for a dishwasher.

Description

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.

The term “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.

It is also necessary that 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.

It must also provide OH- ions, for the saponification of fats and again, for the increase of the negative surface charges of textile surfaces and particulate stains.

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.

Concentrated commercial solutions are most often prepared from completely amorphous silicate called "glassy", also called "water glass".

These soluble glasses are water-solubilized in an autoclave under pressure at 140 ° C. Commercial solutions are thus obtained having a dry extract of about 45% by weight for a silicate of ratio 2 and about 35% for a silicate of ratio 3.5.

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. The silicate, coatomised and co-dried with the other constituents, no longer contains more than 20% of associated water relative to its dry weight, or even less.

As for commercial powder silicate, it is obtained by spray drying of concentrated solutions of glassy silicate; it is necessary to keep 20 to 22% by weight of water relative to the finished product to ensure good solubility of said product.

It has been found that, when dissolved in a washing bath in the proportion of 1 to 3 g / liter, this quine powder silicate contains only 20 to 22% by weight of associated water (relative to the product finished), has only weak builder properties.

Indeed, 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.

Such 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.

What has been observed for a powder containing 20 to 22% of chemically associated water (relative to the finished product) is of course valid for formulations containing a silicate with 20% associated water (relative to dry silicate) prepared by introducing a concentrated solution of silicate into a slurry, then drying.

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.

The expression "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.

• . une solution à 45 % d'extrait sec de silicate vitreux de rapport molaire Si0₂/Na₂0 = 2 contient 34 % d'espèces Q₃, 51 % d'espèces Q₂, 12 % d'espèces 0₁ et 3 % d'espèces Q_o.
• . une solution à 35 % d'extrait sec de rapport 3,5 contient 46 % d'espèces Q₃, 27 % d'espèces Q₂, 16 % d'espèces Q₄, 9 % d'espèces 0₁ et 2 % d'espèces Q_o.

NMR analysis shows that:

• . a 45% solution of dry extract of vitreous silicate with a molar ratio Si0 ₂ / Na ₂ 0 = 2 contains 34% of species Q ₃ , 51% of species Q ₂ , 12% of species 0 ₁ and 3% of species Q _o .
• . a 35% solution of dry extract of ratio 3.5 contains 46% of species Q ₃ , 27% of species Q ₂ , 16% of species Q ₄ , 9% of species 0 ₁ and 2% of 'species Q _o .

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.

The term “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.

Among the 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.

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.

If necessary, 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.

• - on pulvérise une solution aqueuse à base de silicates de métaux alcalins ou à base d'un mélange de silicates et de carbonates de métaux alcalins sur un lit roulant de particules à base de carbonates de métaux alcalins défilant dans un dispositif rotatif de granulation, la vitesse de défilement des particules, l'épaisseur du lit roulant et le débit de la solution pulvérisée étant tels que chaque particule se transforme en un cogranulé plastique en entrant en contact avec d'autres particules,
• - on soumet les cogranulés obtenus à une opération de densification,
• - on sèche lesdits cogranulés densifiés, jusqu'à obtenir une teneur en eau associée au silicate correspondant à un rapport pondéral silicate exprimé en sec/eau associée au silicate de l'ordre de 100/120 à 100/40.

Said spherical cogranules of hydrated alkali metal silicates and alkali metal carbonates can be prepared according to a process characterized in that:

• - An aqueous solution based on alkali metal silicates or based on a mixture of alkali metal silicates and carbonates is sprayed onto a moving bed of particles based on alkali metal carbonates passing through a rotary granulation device, the speed of movement of the particles, the thickness of the moving bed and the flow rate of the sprayed solution being such that each particle is transformed into a plastic cogranulate by coming into contact with other particles,
• - the cogranules obtained are subjected to a densification operation,
• - Said densified cogranules are dried, until a water content associated with the silicate corresponding to a silicate weight ratio expressed in dry / water associated with the silicate of the order of 100/120 to 100/40 is obtained.

Among the 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.

• . un diamètre moyen de l'ordre de 10 à 150 microns, de préférence de l'ordre de 20 à 100 microns et tout particulièrement voisin de 30 à 80 microns,
• . une densité de remplissage non tassée (non bulk density) de l'ordre de 0,4 à 1,1 g/cm3, de préférence de l'ordre de 0,6 à 1,1 g/cm3,
• . une teneur en eau de l'ordre de 0,05 à 0,4%, de préférence de l'ordre de 0,1 à 0,3% en poids,
• . un taux de matières insolubles de l'ordre de 5 à 100 mg/kg, généralement de l'ordre de 10 à 60 mg/kg.

The particles used to prepare the cogranules mainly consist of alkali metal carbonate having:

• . an average diameter of the order of 10 to 150 microns, preferably of the order of 20 to 100 microns and very particularly close to 30 to 80 microns,
• . a non-bulk density of the order of 0.4 to 1.1 g / cm3, preferably of the order of 0.6 to 1.1 g / cm3,
• . a water content of the order of 0.05 to 0.4%, preferably of the order of 0.1 to 0.3% by weight,
• . an insoluble matter level of the order of 5 to 100 mg / kg, generally of the order of 10 to 60 mg / kg.

Common grades, milled or not, of carbonate can be used.

Besides these 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.

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.

• . sa géométrie (troncônique, plat, en escalier, ou combinaison des trois formes),
• . ses dimensions (profondeur, diamètre),
• . son angle d'inclinaison,
• . sa vitesse de rotation,
• . les positions relatives des alimentations en solide et en liquide.

It is within the reach of the skilled person, depending on a given raw material, to adapt the characteristics of the device used to the desired product; to know for a beverage:

• . its geometry (frusto-conical, flat, stepped, or combination of the three forms),
• . its dimensions (depth, diameter),
• . its angle of inclination,
• . its speed of rotation,
• . the relative positions of the solid and liquid supplies.

• . sa géométrie (diamètre du tube)
• . son angle d'inclinaison
• . sa vitesse de rotation
• . la charge du tube
• . les positions relatives des alimentations en solide et en liquide.

For a drum:

• . its geometry (tube diameter)
• . its tilt angle
• . its rotation speed
• . tube load
• . the relative positions of the solid and liquid supplies.

• . une teneur en silicate de l'ordre de 7 à 30 % en poids, de préférence de l'ordre de 11 à 23 % en poids, et tout particulièrement de l'ordre de 21 à 23 % en poids,
• . une teneur en carbonate de l'ordre de 41 à 75 % en poids, de préférence de l'ordre de 48 à 64 % en poids et tout particulèrement de l'ordre de 48 à 51 % en poids,
• . une teneur en eau de l'ordre de 18 à 29 %, de préférence de l'ordre de 25 à 29 %, en poids, et tout particulièrement de l'ordre de 27 à 29 % en poids.

The non-densified and non-dried cogranules obtained have characteristics which depend on the conditions used to produce the granulation. They generally present:

• . a silicate content of the order of 7 to 30% by weight, preferably of the order of 11 to 23% by weight, and very particularly of the order of 21 to 23% by weight,
• . a carbonate content of the order of 41 to 75% by weight, preferably of the order of 48 to 64% by weight and very particularly of the order of 48 to 51% by weight,
• . a water content of the order of 18 to 29%, preferably of the order of 25 to 29%, by weight, and very particularly of the order of 27 to 29% by weight.

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.

• - une teneur en silicate de l'ordre de 8 à 38 % en poids, de préférence de l'ordre de 14 à 31 % en poids, et tout particulièrement de l'ordre de 24 à 31 % en poids,
• - une teneur en carbonate de l'ordre de 47 à 87 % en poids, de préférence de l'ordre de 59 à 81 % en poids, tout particulièrement de l'ordre de 64 à 69 % en poids,
• - une teneur en eau de l'ordre de 5 à 25 % en poids, de préférence de l'ordre de 7 à 20 % en poids, et tout particulièrement de 12 à 20 % en poids,
• - une densité de remplissage non tassée de l'ordre de 0,7 à 1,5 g/cm3 de préférence de l'ordre de 0,75 à 1,5 g/cm3 et tout particulièrement de l'ordre de 0,8 à 1 g/cm3,
• - un diamètre médian (au sens des pourcentages cumulés passants) de l'ordre de 0,4 à 1,8 mm, de préférence de l'ordre de 0,6 à 0,8 mm, avec un écart type log_lO de 0,02 à 0,3, de préférence de 0,05 à 0,1.

Dried dense cogranules generally have:

• a silicate content of the order of 8 to 38% by weight, preferably of the order of 14 to 31% by weight, and very particularly of the order of 24 to 31% by weight,
• a carbonate content of the order of 47 to 87% by weight, preferably of the order of 59 to 81% by weight, very particularly of the order of 64 to 69% by weight,
• a water content of the order of 5 to 25% by weight, preferably of the order of 7 to 20% by weight, and especially from 12 to 20% by weight,
• an unfilled filling density of the order of 0.7 to 1.5 g / cm3, preferably of the order of 0.75 to 1.5 g / cm3 and very particularly of the order of 0.8 at 1 g / cm3,
• - a median diameter (in the sense of the cumulative passing percentages) of the order of 0.4 to 1.8 mm, preferably of the order of 0.6 to 0.8 mm, with a standard deviation log _lO of 0 , 02 to 0.3, preferably 0.05 to 0.1.

These cogranulation / densification / drying stages make it possible to obtain cogranules based on hydrated alkali metal silicates and perfectly spherical, dense and rapidly dissolving alkali metal carbonates.

• - une teneur en silicate de l'ordre de 24 à 31 % en poids,
• - une teneur en carbonate de l'ordre de 64 à 69 % en poids,
• - une teneur en eau de 12 à 20 % en poids,
• - une densité de remplissage non tassé de l'ordre de 0,7 à 1,5 g/cm3, de préférence de l'ordre de 0,8 à 1,
• - un diamètre médian de l'ordre de 0,4 à 0,8 mm, avec écart type log_lO de 0,05 à 0,1.
• - une vitesse de dissolution à 90 % dans l'eau inférieure à 2 minutes et à 95 % inférieure à 4 minutes.

Spherical co-granules based on hydrated sodium silicates and sodium carbonate which are particularly suitable for the preparation of detergent compositions for dishwashing machines and washing machines are those having the following characteristics:

• - a silicate content of the order of 24 to 31% by weight,
• - a carbonate content of the order of 64 to 69% by weight,
• - a water content of 12 to 20% by weight,
• an unfilled filling density of the order of 0.7 to 1.5 g / cm3, preferably of the order of 0.8 to 1,
• - a median diameter of the order of 0.4 to 0.8 mm, with standard deviation log ₁₀ from 0.05 to 0.1.
• - a dissolution rate of 90% in water less than 2 minutes and 95% less than 4 minutes.

The term “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.

When it is structured (powder, co-granulated, etc.) 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).

Next to the builder agent which is the subject of the invention, 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.

• - les agents tensio-actifs anioniques du type savons de métaux alcalins (sels alcalins d'acides gras en C₈
• - C₂₄), sulfonates alcalins (alcoylbenzène sulfonates en C₈ - C₁₃, alcoylsulfonates en C₁₂ - C₁₆), alcools gras en C_s - C₁₆ oxyéthylénés et sulfatés, alkylphénols en C₈ -C₁₃ oxyéthylénés et sulfatés, les sulfosuc- cinates alcalins (alcoylsulfosuccinates en C₁₂ - C₁₆)...
• - les agents tensio-actifs non ioniques du type alcoylphénols en C_s - C₁₂ polyoxyéthylénés, alcools aliphatiques en C₈ - C₂₂ oxyéthylénés, les copolymères bloc oxyde d'éthylène - oxyde de propylène, les amides carboxyliques éventuellement polyoxyéthylénés,
• - les agents tensio-actifs amphotères du type alcoyldiméthylbétaïnes,
• - les agents tensio-actifs cationiques du type chlorures ou bromures d'alkyltriméthylammonium, d'alkyldi- méthyléthylammonium. Divers constituants peuvent en outre être présents dans la composition lessivielle tels que :
• - des "builders" du type :
  • . phosphates à raison de moins de 25 % du poids total de formulation,
  • . zéolithes jusqu'à environ 40 % du poids total de formulation,
  • . carbonate de sodium jusqu'à environ 80 % du poids total de formulation,
  • . acide nitriloacétique jusqu'à environ 10 % du poids total de formulation,
  • . acide citrique, acide tartrique jusqu'à environ 20 % du poids total de formulation, la quantité totale de "builder" correspondant à environ 0,2 à 80 %, de préférence de 20 à 45 % du poids total de ladite composition détergente,
• - des agents de blanchiment du type perborates, percarbonates, chloroisocyanurates, N, N, N', N'-tétraa- cétyléthylènediamine (TAED) jusqu'à environ 30 % du poids total de ladite composition détergente,
• - des agents anti-redéposition du type carboxyméthylcellulose, méthylcellulose en quantités pouvant aller jusqu'à environ 5 % du poids total de ladite composition détergente,
• - des agents anti-incrustation du type copolymères d'acide acrylique et d'anhydride maléïque en quantité pouvant aller jusqu'à 10 % environ du poids total de ladite composition détergente,
• - des charges du type sulfate de sodium pour les détergents en poudre en quantité pouvant aller jusqu'à 50 % du poids total de ladite composition détergente.

Among these surfactants, mention may be made of:

• - anionic surfactants of the alkali metal soap type (alkaline salts of C ₈ fatty acids
• - C _24), alkali metal sulfonates (alkylbenzene sulfonates, C ₈ - C ₁₃ alkyl sulfonates, C ₁₂ - C ₁₆₎ fatty alcohols, C _s - C ₁₆ ethoxylated and sulphated alkylphenols, C ₈ -C ₁₃ ethoxylated and sulfated, the alkali sulfosuccinates (C ₁₂ -C ₁₆ alkyl sulfosuccinates) ...
• non-ionic surfactants of the polyoxyethylenated C _s -C ₁₂ alkylphenols type, oxyethylenated C ₈ -C ₂₂ aliphatic alcohols, ethylene oxide-propylene oxide block copolymers, optionally polyoxyethylenated carboxylic amides,
• - amphoteric surfactants of the alkyldimethylbetaines type,
• - cationic surfactants of the chlorides or bromides type of alkyltrimethylammonium, of alkyldimethylethylammonium. Various constituents can also be present in the detergent composition such as:
• - "builders" of the type:
  • . phosphates at a rate of less than 25% of the total weight of the formulation,
  • . zeolites up to around 40% of the total formulation weight,
  • . sodium carbonate up to approximately 80% of the total formulation weight,
  • . nitriloacetic acid up to about 10% of the total formulation weight,
  • . citric acid, tartaric acid up to approximately 20% of the total weight of formulation, the total amount of "builder" corresponding to approximately 0.2 to 80%, preferably from 20 to 45% of the total weight of said detergent composition,
• bleaching agents of the perborate, percarbonate, chloroisocyanurate, N, N, N ', N'-tetraacetylethylenediamine (TAED) type up to around 30% of the total weight of said detergent composition,
• - anti-redeposition agents of the carboxymethylcellulose, methylcellulose type in amounts which can range up to approximately 5% of the total weight of said detergent composition,
• anti-encrustation agents of the acrylic acid and maleic anhydride copolymer type in an amount which can range up to approximately 10% of the total weight of said detergent composition,
• - fillers of the sodium sulfate type for powdered detergents in an amount which can range up to 50% of the total weight of said detergent composition.

The following examples are given for information only and cannot be considered as limiting the scope and spirit of the invention.

EXAMPLES 1 to 5

• - d'une solution de silicate de sodium de rapport molaire Si0₂/Na₂0 = 2 à 45 % en poids d'extrait sec (exemple 2)
• - d'une solution de silicate de sodium de rapport molaire Si0₂/Na₂0 = 3,4 à 35 % en poids d'extrait sec (exemple 4) sont mesurées dans un TERGOTOMETRE (US Testing Company, Hoboken, USA), en mélange binaire avec un surfactant anionique LABS (dodecyl benzène sulfonate de sodium linéaire de ALDRICH), les mesures de réflectance étant réalisées à l'aide d'un reflectomètre GARDNER.

"Builder" performances

• - a sodium silicate solution with a molar ratio Si0 ₂ / Na ₂ 0 = 2 to 45% by weight of dry extract (example 2)
• a sodium silicate solution with a molar ratio Si0 ₂ / Na ₂ 0 = 3.4 to 35% by weight of dry extract (example 4) are measured in a TERGOTOMETER (US Testing Company, Hoboken, USA), in binary mixture with an anionic LABS surfactant (linear sodium dodecyl benzene sulfonate from ALDRICH), the reflectance measurements being carried out using a GARDNER reflectometer.

• - du LABS seul à 2 g/I (exemple 1)
• - d'une poudre atomisée de silicate de rapport 2 contenant 22 % d'eau (soit 28,2 % d'eau par rapport au silicate sec) (exemple 3)
• - d'une poudre atomisée de silicate de rapport 3,4 contenant 18,6 % d'eau (soit 22,8 % d'eau par rapport au silicate sec) (exemple 5) mises en oeuvre dans les mêmes conditions (4 g/I).

These performances are compared to those:

• - LABS alone at 2 g / I (example 1)
• - an atomized powder of silicate of ratio 2 containing 22% of water (i.e. 28.2% of water relative to the dry silicate) (example 3)
• an atomized powder of silicate of ratio 3.4 containing 18.6% of water (ie 22.8% of water relative to the dry silicate) (example 5) used under the same conditions (4 g / I).

The results of these measurements are shown in Table 1

Measurement method Principle:

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.

Operating mode:

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.

1) In each pot we put 11 hard tap water (34 ° TH French)

• - 5 éprouvettes de 10 X 12 cm de coton blanc style 405 W de la société TEST FABRIC.
• - 5 éprouvettes de 10 X 12 cm de polyestercoton (PEC) blanc de référence n°7435 de la société TEST FABRIC.
• - 2 éprouvettes de 10 X 12 cm de coton sali EMPA (mélange d'encre de chine et d'huile d'olive) article 101 de la société GALLEN.
• - 2 éprouvettes de 10 X 12 cm de coton sali vin rouge article 114 de la société GALLEN.
• - 2 éprouvettes de 10 X 12 cm de polyestercoton (PEC) sali EMPA article 104 de la société GALLEN.

When the water is at temperature, we introduce:

• - 5 test tubes of 10 X 12 cm of white cotton style 405 W from the company TEST FABRIC.
• - 5 test pieces of 10 X 12 cm white polyestercotton (PEC) reference n ° 7435 from the company TEST FABRIC.
• - 2 test tubes of 10 X 12 cm of soiled cotton EMPA (mixture of Chinese ink and olive oil) article 101 of the company GALLEN.
• - 2 test tubes of 10 X 12 cm of cotton soiled red wine article 114 of the company GALLEN.
• - 2 test tubes of 10 X 12 cm of polyestercotton (PEC) soiled EMPA article 104 of the company GALLEN.

2) The following 3 operations are carried out simultaneously:

• . stopwatch start
• . start of agitation
• . addition of builder / surfactant mixture

The builder is tested at 4 g / I (mass counted as dry matter of product) and 2 g / I of LABS are added thereto.

3) Rinsing

When twenty minutes have passed, the wash water is thrown away and the fabrics are rinsed with 3 X 11 cold tap water.

4) Spinning and drying

The 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.

5) Color measurement

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.

• L = 100 correspond à éprouvette blanche
• L = 0 correspond à éprouvette noire
  • a situe la couleur dans les teintes du vert au rouge.
    • a > o : la couleur tire sur le rouge
    • a < o : la couleur tire sur le vert
  • b situe la couleur dans les teintes du jaune au bleu.
    • b > o : la couleur tire sur le jaune
    • b < o : la couleur tire sur le bleu

L places the color in shades from white to black.

• L = 100 corresponds to white test tube
• L = 0 corresponds to black test tube
  • located the color in shades from green to red.
    • a> o: the color turns to red
    • a <o: the color turns to green
  • b locates the color in shades from yellow to blue.
    • b> o: the color turns to yellow
    • b <o: the color turns to blue

After calibration, the actual measurements are made. By pot we take 2 test tubes from each category of fabrics, we make 5 measurements per test tube (that is to say one in the center and one at the four corners) by placing on the fabric a heavy metal plate, then we make the arithmetic mean of the 10 determinations. We proceed in the same way with unwashed fabrics.

6) Exploitation of results

• DL = L après lavage - L avant lavage
• Da = a avant lavage - a après lavage
• Db = b avant lavage - b après lavage
• DE =-IDL2 ₊ D_a2 + Db² = Détergence

DL and DE are calculated for each test and for each type of tissue.

• DL = L after washing - L before washing
• Da = a before washing - a after washing
• Db = b before washing - b after washing
• DE = -IDL2 ₊ D _a 2 + Db ² = Detergency

The average DL and DE is calculated for each product and each type of soiled tissue.

• Dét(ergence) coton EMPA = DE moyen coton EMPA
• Dét(ergence) PEC EMPA = DE moyen PEC EMPA
• Dét(ergence) coton VIN = DE moyen coton VIN
• Dét(ergence) cumulée = Somme des détergences coton EMPA, PEC EMPA, coton VIN

Then for each product, we calculate:

• EMPA cotton det (ergonomics) = EMPA medium cotton
• Det (ergonomics) PEC EMPA = DE average PEC EMPA
• Det (ergonomics) cotton VIN = DE medium cotton VIN
• Cumulative det (ergence) = Sum of detergents cotton EMPA, PEC EMPA, cotton WINE

EXAMPLES 6 and 7

A LODIGE M5G @ mixer (sold by LODIGE) is loaded with 800 g of anhydrous tripolyphosphate H ₂ @ sold by Rhône-Poulenc.

After closing and rotating the apparatus at a speed of 400 rpm, 200 g of a sodium silicate solution with a molar ratio Si0 ₂ / Na ₂ 0 = 2 to 45% of extract are introduced by spraying. dry.

This addition lasts 10 min; after an additional 10 min of mixing per rotation, the product is removed and left to stand for 2 h on a tray in the open air and at room temperature.

• - TPP partiellement hydraté : 82 % en poids
• - silicate de sodium : 9 % en poids
• - eau associée au silicate : 9 % en poids, soit 100 % par rapport au silicate sec.

The product features are:

• - TPP partially hydrated: 82% by weight
• - sodium silicate: 9% by weight
• - water associated with silicate: 9% by weight, ie 100% relative to dry silicate.

• - diamètre moyen = 250 micromètres

The amount of total water contained in the product is determined by measuring the weight loss of the latter by heating to 500 ° C .; on the other hand, the quantity of bound water in the form of hydrates is measured by differential thermal analysis. The amount of associated water is calculated by the difference between total water and bound water in the form of hydrate.

• - average diameter = 250 micrometers

The "builder" performances of this product are measured according to the method described above, however replacing the 2 PEC dirty EMPA test pieces article 104 with 2 dirty cotton WFK test pieces from the company KREFELD, of the same dimensions (example 6).

These performances are compared with those of a mixture of anhydrous TPP powders H ₂ @ and of atomized silicate of Si0 ₂ / Na ₂ 0 ratio = 2 to 22% water, according to a weight ratio TPP / dry silicate of 800 / 90, and this under the same conditions (4 g / I) (example 7).

The results of the measurements are shown in Table II.

EXAMPLE 8

• - Titre en alcalinité : 99,61 %
• - teneur en eau (en poids) = 0,12 %
• - densité de remplissage non tassée = 0,56g/cm3
• - diamètre médian = 95 microns
• - taux d'insolubles = 58 mg/kg

The granulation system consists of a flat plate with a diameter of 800 mm and a depth of 100 mm. During granulation, the speed of rotation is of the order of 35 rpm and the inclination of the axis of rotation relative to the horizontal is of the order of 55 °. The pellet plate is continuously fed at a rate of 21.4 kg / h by a powder made up of fine particles of sodium carbonate, the main characteristics of which are as follows:

• - Title in alkalinity: 99.61%
• - water content (by weight) = 0.12%
• - unfilled filling density = 0.56g / cm3
• - median diameter = 95 microns
• - insoluble rate = 58 mg / kg

On this powder brought into rotation in the granulating dish is sprayed with air at 80 ° C a solution of sodium silicate at a rate of 13.4 I / h at a temperature of 80 ° C per l 'through a bi-fluid nozzle located at a distance of 20 cm from the bottom of the bezel. The active material content and the Si0 ₂ / Na ₂ 0 molar ratio of the sprayed solution are 43% (by weight) and 2, respectively.

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.

• - teneur en carbonate (en poids) = 65 %
• - teneur en silicate (en poids) = 21 % ± 0,5 %
• - teneur en eau (en poids) = 13,5 %
• - densité de remplissage non tassée = 0,90 g/cm3
• - % en poids de refus à 1 mm = 10,8 %
• - diamètre médian = 0,73 mm
• - % en poids de passant à 0,2 mm = 6 %
• - 90 % (en poids) du produit se dissout en 50 s (solution aqueuse à 35 g/I à 20°C),
• - 95 % (en poids) du produit se dissout en 65 s (solution aqueuse à 35 g/I à 20°C),
• - blancheur L = 96,3
• - résistance à l'attrition : 7 %,

The product thus dried has the following characteristics:

• - carbonate content (by weight) = 65%
• - silicate content (by weight) = 21% ± 0.5%
• - water content (by weight) = 13.5%
• - filling density not packed = 0.90 g / cm3
• -% by weight of refusal at 1 mm = 10.8%
• - median diameter = 0.73 mm
• -% by weight from 0.2 mm = 6%
• - 90% (by weight) of the product dissolves in 50 s (aqueous solution at 35 g / I at 20 ° C),
• - 95% (by weight) of the product dissolves in 65 s (35 g / l aqueous solution at 20 ° C),
• - whiteness L = 96.3
• - attrition resistance: 7%,

The granules exhibit excellent storage behavior.

Measurement of attrition resistance: Material:

We use the flourometer, a standardized device used to qualify hydraulic binders and described in French standard P 15-443.

• Tamiser 50g de produit entre le tamis 1200 et 180 microns, à l'aide d'une tamiseuse de laboratoire RO-TO-LAB @ (commercialisée par PROLABO).

Procedure:

• Sieve 50g of product between the 1200 and 180 micron sieve, using a RO-TO-LAB @ laboratory sieve shaker (marketed by PROLABO).

Recover the part between 180 and 1200 microns

Weigh approximately exactly 25 g of the product to be tested; let M be the exact mass.

Place them in the flourometer.

Weigh an empty and dry Soxlhet 0 type filter (marketed by PROLABO) and place it at the top of the fluidization tube; let M1 be its mass.

Fluidize for 5 min (dry air flow: 15 I / min).

Recover the product flown in the filter as well as any fines deposited on the vertical walls of the fluidization tube, using a swab of suitable diameter. Weigh ; let M2 be the mass of these fine and filter.

Sieve again on ROTO LAB @ the residue in the bottom of the fluidization tube and recover, for weighing, fines smaller than 180 microns; let M3 be the mass of these fines.

• Le taux d'attrition est égal au pourcentage de fines < 180 microns formé pendant le temps de fluidisation du produit.
  

Calculation. Expression of the result:

• The attrition rate is equal to the percentage of fines <180 microns formed during the fluidization time of the product.
  

Example 9:

The operations described in Example 1 are repeated, with the only following modifications:

Granulation:

• . pellet plate: rotation speed of 30 rpm,
• . powder feed: 22kg / h,
• . supply of silicate solution: 13 i / h.

Densification:

. drum rotation speed: 10 rpm,

Fluid bed drying:

• . temperature = 90 ° C,
• . duration: 20 min,

• - teneur en carbonate (en poids) = 60,9 %,
• - teneur en silicate (en poids) = 22,9 % ± 0,5 %,
• - teneur en eau (en poids) = 16,1 %
• - densité de remplissage non tassée = 0,86 g/cm3
• - % en poids de refus à 1 mm = 2,6 %
• - diamètre médian = 0,64 mm
• - % en poids de passant à 0,2 mm= 7,3 %
• - 90 % (en poids) du produit se dissout en 75 s (solution aqueuse à 35 g/I à 20 °C),
• - 95 % (en poids) du produit se dissout en 102 s (solution aqueuse à 35 g/I à 20°C),
• - blancheur L = 95,6
• - résistance à l'attrition : 9,2 %

The dried product has the following characteristics:

• - carbonate content (by weight) = 60.9%,
• - silicate content (by weight) = 22.9% ± 0.5%,
• - water content (by weight) = 16.1%
• - unfilled filling density = 0.86 g / cm3
• -% by weight of refusal at 1 mm = 2.6%
• - median diameter = 0.64 mm
• -% by weight from 0.2 mm = 7.3%
• - 90% (by weight) of the product dissolves in 75 s (35 g / I aqueous solution at 20 ° C),
• - 95% (by weight) of the product dissolves in 102 s (35 g / I aqueous solution at 20 ° C),
• - whiteness L = 95.6
• - attrition resistance: 9.2%

The granules exhibit excellent storage behavior.

Example 10:

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.

On this powder brought into rotation in the drum, is sprayed with air at 80 ° C via a bi-fluid nozzle with flat jet located at the first third of the drum, a silicate solution (having an active material content of 45.6% by weight and a Si0 ₂ / Na ₂ 0 weight ratio of 2) at 80 ° C. with a flow rate of 18 I / h.

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.

• - teneur en carbonate (en poids) = 62 %,
• - teneur en silicate (en poids) = 20,5 % ± 0,5 %,
• - teneur en eau (en poids) = 17,6 %
• - densité de remplissage non tassée = 0,820
• - % en poids de refus à 1 mm = 5 %,
• - diamètre médian = 0,65 mm
• - % en poids de passant à 0,2 mm = 0,6 %
• - 90 % (en poids) du produit se dissout en 50 s (solution aqueuse à 35 g/I à 20°C),
• - 95 % (en poids) du produit se dissout en 63 s (solution aqueuse à 35 g/I à 20°C),

The dried product has the following characteristics:

• - carbonate content (by weight) = 62%,
• - silicate content (by weight) = 20.5% ± 0.5%,
• - water content (by weight) = 17.6%
• - filling density not packed = 0.820
• -% by weight of refusal at 1 mm = 5%,
• - median diameter = 0.65 mm
• -% by weight from 0.2 mm = 0.6%
• - 90% (by weight) of the product dissolves in 50 s (aqueous solution at 35 g / I at 20 ° C),
• - 95% (by weight) of the product dissolves in 63 s (35 g / I aqueous solution at 20 ° C),

The granules exhibit excellent storage behavior.

Example 11:

The operations described in Example 3 are repeated, with the only following modification:

Densification:

. discontinuously for 2 hours.

• - teneur en carbonate (en poids) = 60,8 %,
• - teneur en silicate (en poids) = 19,3 % ± 0,5 %,
• - teneur en eau (en poids) = 19,9 %
• - densité de remplissage non tassée = 0,91 g/cm3
• - % en poids de refus à 1 mm = 1,6 %,
• - diamètre médian = 0,57 mm
• - % en poids de passant à 0,2 mm = 1,22 %
• - 90 % (en poids) du produit se dissout en 37 s (solution aqueuse à 35 g/I à 20°C),
• - 95 % (en poids) du produit se dissout en 45 s (solution aqueuse à 35 g/I à 20°C),

The dried product has the following characteristics:

• - carbonate content (by weight) = 60.8%,
• - silicate content (by weight) = 19.3% ± 0.5%,
• - water content (by weight) = 19.9%
• - unfilled filling density = 0.91 g / cm3
• -% by weight of refusal at 1 mm = 1.6%,
• - median diameter = 0.57 mm
• -% by weight from 0.2 mm = 1.22%
• - 90% (by weight) of the product dissolves in 37 s (35 g / I aqueous solution at 20 ° C),
• - 95% (by weight) of the product dissolves in 45 s (35 g / I aqueous solution at 20 ° C),

The granules exhibit excellent storage behavior.

Examples 12 and 13

The “builder” performances of the cogranules of Example 8 are measured according to the method described in Examples 1 to 5.

They are compared with those of a mixture of sodium carbonate powder and atomized sodium silicate powder of Si0 ₂ / Na ₂ 0 = 2 ratio containing 22% water in the finished product (i.e. 28.2% d water relative to dry silicate) in a weight ratio 3/1 (carbonate / R ₂ atomized).

The results are shown in Table III.

The amounts of carbonate and silicate shown in this table are expressed in dry.

It can be seen that the performance of the cogranules is better than that of a mixture of powders having the same silicate / carbonate ratio.

Example 14

• - 1800 g de carbonate de soude léger en poudre, présentant un diamètre moyen de l'ordre de 110 µm
• - 1200 g de solution de silicate de sodium de rapport molaire Si0₂/Na₂0 = 3,4 à 37 % d'extrait sec.

Particles are prepared from a LODIGE M5G @ mixer, according to the procedure of Examples 6 and 7:

• - 1800 g of light powdered sodium carbonate, with an average diameter of the order of 110 μm
• - 1200 g of sodium silicate solution with a molar ratio Si0 ₂ / Na ₂ 0 = 3.4 to 37% of dry extract.

• - carbonate de sodium : 60 % en poids
• - silicate = 20 % en poids
• - eau associée au silicate = 20 % en poids (soit 100 % par rapport au silicate sec).
• - diamètre moyen = 400 µm

After 5 minutes of addition of the silicate solution, additional 5 minutes of mixing and stay in the open air for 2 hours at room temperature, a product is recovered whose characteristics are as follows:

• - sodium carbonate: 60% by weight
• - silicate = 20% by weight
• - water associated with silicate = 20% by weight (i.e. 100% relative to dry silicate).
• - average diameter = 400 µm

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.

• - cycle utilisé : 60°C
• - durée totale du cycle : 70 minutes ; pas de prélavage
• - nombres de cycles : 3 par lessive
• - dureté de l'eau : 32 degrés hydrotimétriques français
• - charge de linge : 3,5 kg de torchons en coton blanc
• - tissus testés : par lavage, on introduit, en les épinglant sur torchons, deux séries de tissus suivants :
  • Coton gris : Test-Fabric Krefeld 10 C IEC 106
  • EMPA 101 Polyester/coton gris : Test-Fabric Krefeld 20 C EMPA 104
  • Taches protéiniques : Sang (EMPA 111) Cacao (EMPA 112) Mixte (EMPA 116)
  • Taches oxydables : Thé (Krefeld 10 G) Coton écru (EMPA 222) Vin (EMPA 114)
• - Doses de lessives :
  • 1 ère série : 5 g/I soit 5 x 20 = 100 g par lavage
  • 2ème série : 8 g/I soit 8 x 20 = 160 g par lavage

The test conditions are as follows:

• - cycle used: 60 ° C
• - total cycle time: 70 minutes; no prewash
• - number of cycles: 3 per detergent
• - water hardness: 32 French hydrotimetric degrees
• - load of linen: 3.5 kg of white cotton tea towels
• - fabrics tested: by washing, we introduce, by pinning them on cloths, two series of following fabrics:
  • Gray cotton: Test-Fabric Krefeld 10 C IEC 106
  • EMPA 101 Polyester / cotton gray: Test-Fabric Krefeld 20 C EMPA 104
  • Protein stains: Blood (EMPA 111) Cocoa (EMPA 112) Mixed (EMPA 116)
  • Oxidizable stains: Tea (Krefeld 10 G) Unbleached cotton (EMPA 222) Wine (EMPA 114)
• - Doses of detergents:
  • 1 st series: 5 g / I, i.e. 5 x 20 = 100 g per wash
  • 2nd series: 8 g / I, i.e. 8 x 20 = 160 g per wash

Method for measuring the removal of dirt and stains

Photometric measurements (measurements of the amount of light reflected by the fabric) make it possible to calculate the percentages of soil removal. We use the ELREPHO 2000 device from DATACALOR.

où

• A = réflectance de l'échantillon blanc témoin
• B = réflectance de l'échantillon sali témoin
• C = réflectance de l'échantillon sali après lavage

The elimination of soiling is expressed by the formula:

or

• A = reflectance of the blank control sample
• B = reflectance of the soiled control sample
• C = reflectance of the soiled sample after washing

• Nombre de mesures effectuées par échantillon = 4
• Nombre d'échantillons par lavage = 2
• Nombre de lavages 3 3

The reflectances are determined using the blue trichromatic component, without the action of optical brighteners.

• Number of measurements made per sample = 4
• Number of samples per wash = 2
• Number of washes 3 3

Or 4 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.

• - cycle utilisé : 60°C
• - durée totale du cycle = 65 minutes ; pas de prélavage
• - nombre de cycles : 25 lavages cumulés
• - dureté de l'eau : 21,2 degrés hydrotimétriques français
• - tissu test utilisé : bande témoin répondant exactement aux spécifications développées dans la norme NFT 73.600
• - charge de linge : 3 kg de serviettes éponges 100 % coton
• - doses de lessive : 5 g/I

The test conditions are as follows:

• - cycle used: 60 ° C
• - total cycle time = 65 minutes; no prewash
• - number of cycles: 25 cumulative washes
• - water hardness: 21.2 French hydrotimetric degrees
• - test fabric used: control strip exactly meeting the specifications developed in standard NFT 73.600
• - laundry load: 3 kg of 100% cotton terry towels
• - detergent doses: 5 g / I

The 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.

The results of the various tests are shown in Table IV.

Example 15

• . zeolithe 4A 30 parties
• . silicate R₂ atomisé 3
• . carbonate léger 6
• . sulfate de sodium 4,8
• . SOKALAN CP5 4

A detergent analogous to that of Example 14 is prepared by replacing the “builder” mixture zeolite 4A + product of Example 14 + SOKALAN CP5 with the following “builder” mixture:

• . zeolite 4A 30 parts
• . silicate R ₂ atomized 3
• . light carbonate 6
• . sodium sulfate 4.8
• . SOKALAN CP5 4

The results of the dirt removal and anti-scaling tests are shown in Table IV.

Examples 16-18

The product of Example 8 is introduced by mixing into a LODIGE M5G @ with additives in order to obtain compositions for dishwashers.

These compositions are listed in Table V.

These 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.

With each composition used at 3 g / liter of water, 10 cumulative soda-lime glass plates are washed, initially perfectly clean.

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.

When L is between 4 and 7, the result is considered to be very good, the glass is clear.

When L is between 7 and 14, a slight haze is visible.

The product of Example 8 is compared in a fairly similar formulation to a mixture of sodium carbonate cogranules and BRITSIL H20 @ cogranules (of Si0 ₂ / _Na2 0 = 2 ratio and containing 20% water - sold by Philadelphia Quartz).

The results are shown in Table V.

It is found that the use of cogranules from Example 8 makes it possible to reduce the amount of sodium citrate (expensive) and polyacrylate (non-biodegradable).

Claims (28)

1) "Builder" agent for detergent composition, characterized in that it consists of an alkali metal silicate, in particular of sodium or potassium, containing at least 30% of silicon atoms in Q ₂ and Q _{3 form} . 2) "Builder" agent according to claim 1 characterized in that it consists of an alkali metal silicate, in particular of sodium or potassium, containing at least 50% of silicon atoms in the form Q ₂ and Q ₃ . 3) "Builder" agent according to claim 1 or 2, characterized in that it consists of an aqueous solution of approximately 10-60% by weight of dry extract of an alkali metal silicate, in particular of sodium or potassium, of Si0 ₂ / M ₂ 0 molar ratio of the order of 1.6 to 3.5. 4) "Builder" agent according to claim 1 or 2, characterized in that it consists of an aqueous solution of approximately 10-60% by weight of dry extract of an alkali metal silicate, in particular of sodium or potassium, Si0 ₂ / M ₂ 0 molar ratio can range from 1.6 to 3.5, adsorbed and / or absorbed on a particulate support inert with respect to silicate, the silicate weight ratio expressed in dry / water remaining associated with silicate ranging from 100/120 to 100/40. 5) Agent "builder" according to claim 4 characterized in that the support represents from 55 to 95% of the weight of the supported solution expressed in dry. 6) Agent "builder" according to claim 4 or 5 characterized in that said support is sodium carbonate, sodium sulfate, sodium borate, sodium perborate, sodium metasilicate, a phosphate or polyphosphate such as trisodium phosphate, sodium tripolyphosphate ..., or a mixture of these salts. 7) Process for preparing the builder agent which is the subject of any one of claims 4 to 6 by adsorption and / or absorption by bringing into contact a concentrated aqueous solution of a silicate of a metal alkaline with Si0 ₂ / M ₂ 0 molar ratio of the order of 1.6 to 3.5, and having a dry extract of the order of 10 to 60%, with an inorganic support inert 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 . 8) A method according to claim 7 characterized in that the contacting operation is carried out by spraying said concentrated silicate solution on the support in particulate form at a temperature of the order of 20 to 95 ° C. 9) Spherical cogranules of hydrated alkali metal silicates and alkali metal carbonate, capable of being obtained according to a process characterized in that: - An aqueous solution based on alkali metal silicates or based on a mixture of alkali metal silicates and carbonates is sprayed onto a moving bed of particles based on alkali metal carbonates passing through a rotary granulation device, the speed of movement of the particles, the thickness of the moving bed and the flow rate of the sprayed solution being such that each particle is transformed into a plastic cogranulate by coming into contact with other particles. - the cogranules obtained are subjected to a densification operation, - Said densified cogranules are dried, until a water content associated with the silicate corresponding to a silicate weight ratio expressed in dry / water associated with the silicate of the order of 100/120 to 100/40 is obtained. 10) Cogranules according to claim 9, characterized in that the aqueous solution based on silicate or of pulverized silicate / carbonate mixture has a dry extract content of the order of 30 to 55% by weight, said alkali metal silicate having a Si0 ₂ / M20 molar ratio of the order of 1.6 to 3.5, said carbonate possibly being present in proportions depending on the desired final product. 11) Cogranules according to claim 9 or 10 characterized in that the spraying of the solution based on silicate or silicate / carbonate mixture is carried out at a temperature of the order of 20 to 95 ° C. 12) Cogranules according to any one of claims 9 to 11 characterized in that the particles constituting the moving bed are based on an alkali metal carbonate having: . an average diameter of the order of 10 to 150 microns, . an uncompressed filling density of the order of 0.4 to 1.1 g / cm3, . a water content of the order of 0.05 to 0.4%, . an insoluble matter rate of the order of 5 to 100 mg / kg. 13) Co-granules according to any one of Claims 9 to 12, characterized in that the particles constituting the moving bed contain less than 10% of the weight of the co-granules of particles of a nature other than an alkali metal carbonate and having a diameter and a density close to that of the alkali metal carbonate particles. 14) Co-granules according to any one of Claims 9 to 13, characterized in that the granulation device is a rotary granulator allowing the particles to travel in a thin layer. 15) Cogranules according to claim 14 characterized in that the rotary granulator is a bezel. 16) Cogranules according to any one of claims 9 to 13 characterized in that the granulation device is a drum. 17) Granules according to any one of claims 9 to 16 characterized in that the carbonate-based particles pass at a temperature of the order of 15 to 200 ° C. 18) Granules according to any one of claims 9 to 17, characterized in that the quantities of silicate-based solution or silicate / carbonate mixture to be sprayed and of carbonate-based particles to be used correspond to a flow rate ratio of liquid / particle flow rate ranging from 0.2 to 0.8 I / kg, these values being expressed as sodium salts. 19) Cogranules according to any one of claims 9 to 18 characterized in that the densification operation is carried out at ambient temperature by rolling the cogranules obtained in the granulation step in a rotary device. 20) Cogranules according to claim 19 characterized in that the densification operation is carried out in a rotary drum. 21) Cogranules according to any one of claims 9 to 20 characterized in that the cogranules obtained after densification are dried in a fluidized bed. 22) Cogranules according to any one of claims 9 to 21 characterized in that the cogranules obtained after drying are added, by spraying, small amounts of liquid compounds commonly used in the field of detergency. 23) Spherical co-granules based on alkali metal silicates and alkali metal carbonates, characterized in that they have: a silicate content of molar ratio Si0 ₂ / M ₂ 0 of 1.6 to 3.5, of the order of 8 to 38% by weight, - a carbonate content of the order of 47 to 87% by weight, - a water content of the order of 5 to 25% by weight, - an uncompressed filling density of the order of 0.7 to 1.5 g / cm3, - a median diameter of the order of 0.4 to 1.8 mm, with a standard deviation log _l0 of 0.02 to 0.3. 24) Spherical co-granules of hydrated sodium silicate and sodium carbonate, characterized in that they have: a silicate content of SiO ₂ / Na ₂ 0 molar ratio of 1.8 to 2.6, of the order of 24 to 31% by weight, - a carbonate content of the order of 64 to 69% by weight, - a water content of 12 to 20% by weight, - an uncompressed filling density of the order of 0.7 to 1.5 g / cm3, preferably of the order of 0.8 to 1. - a median diameter of the order of 0.4 to 0.8 mm, with a standard deviation log _l0 of 0.05 to 0.1. - a dissolution rate of 90% in water less than 2 minutes and 95% less than 4 minutes. 25) "Builder" agent consisting of the cogranules forming the subject of any one of claims 9 to 24. 26) Use of the "builder" agent which is the subject of claim 3 in detergent powder compositions, in post-addition by spraying onto the detergent powder at the bottom of the tower or on a mixture of components of formula detergent, the dry silicate / powder weight ratio or detergent formula being between 1/100 and 30/100 and the dry silicate / water weight ratio remaining associated with the silicate between 100/120 and 100/40. 27) Use of the "builder" agent which is the subject of any one of claims 4 to 8 and 25 in powdered detergent compositions for dishwashing machines in a proportion of 3 to 90% by weight of dry silicate compared to the composition. 28) Use of the "builder" agent which is the subject of any one of claims 4 to 8 and 25 in detergent powder compositions for washing machines in a proportion of 3 to 60% by weight of dry silicate relative to to the composition.