RO110009B1 - "builder" forming agent on the silicates of the alkaline metals basis for detergent compositions and preparation processes therefor - Google Patents

Abstract

The structureforming agent is designed for powder detergentsubstances applicable is washing lines and dishwasing machines. Itis formed by a silicate of a silicon-rich alkaline metal, in theform of Q2 and Q3. The solution of the alkaline metal silicate inratio between SiO2 to M2O of 1.0 to 3.5 is produced with drymatter form 10 to 80% or in a form for application, especially inthe form of cogranulates. The weight ratio between the silicate inthe form of dry matter and water bound to it is from 100:120 to100:40.28 claims

Description

The present invention relates to a builder forming agent, consisting of alkali metal silicates, rich in compounds in which the silicon atoms are in the form of Q ₂ and Q ₃ , this agent being intended for use in solid detergent compositions, especially in the form. powder for washing machines or dishes, and in the process of obtaining this agent.

By training agent is meant that active adjuvant which improves the performance of the surface active agent in a detergent composition.

The forming agent has the role of reducing the hardness of the water used for washing. It removes the calcium and magnesium ions present in water as soluble salts and removes dirt from the laundry, as more or less soluble cornflakes. The elimination of calcium and magnesium ions can be done either by complexation, in the form of soluble compounds, or by ion exchangers or precipitation.

If the precipitation technique is applied, then the process must be well controlled so that it does not become embedded on the laundry or on the surfaces of the washing machine. In general, for the precipitation of calcium and magnesium ions, water-soluble polymers that have affinity to these ions are used.

Another role of the forming agent is to improve the emulsifying effect of the surfactant against greasy dirt, as well as dispersion against pigmented dirt such as: metal oxides, clays, silica, various forms of dust , humus, limestone, soot etc.

This dispersing effect is generally obtained due to the presence of polyanions, which ensures the density of negative charges at the interface.

Also, the formation agent must provide the ionic charge specific to the action of the surfactant, contributing mainly to the increase of mycelium size.

At the same time, it must provide hydroxyl ion concentrations, necessary for the saponification of fats, as well as for the increase of the superficial negative charge of the surfaces of textiles and dirt particles.

Silicates are considered to be the best detergent adjuvants (washing power), but at present they are less used in phosphate-free detergent compositions for washing machines.

In these situations, the most used silicates are those compounds whose molar ratio SiO ₂ / Na ₂ O is between 1.6 and 2.4. These silicates are marketed in the form of concentrated solutions, having a content of substance extracted of approx.

35 .. .45% or as atomized and possibly compacted powder.

Concentrated commercial solutions are most often prepared using amorphous silicates, called soluble bottles, as feedstocks.

These silicates are water solubilized in autoclaves, under pressure and, temperatures of 140'C. This gives the concentrated solutions, characterized by a content of dry extracted substance, of 45% by weight, for the assortment of silicate whose molar ratio SiOj / NajO is 2 and 35% by weight, for the assortment whose molar ratio SiO ₂ / NajO is 3.5.

Concentrated silicate solutions are introduced into the detergent compositions in the form of aqueous suspensions (slurry), together with other ingredients of the detergent composition. The aqueous suspension is sprayed.

Silicate sprayed with other ingredients contains approx. 20% water, relative to the dry matter, or even less.

Silicates marketed as »9 powders are obtained by spraying concentrated solutions of soluble glass silicates; is indicated to maintain a content of 9,

20 .. .22% by weight of water relative to the finished product, to ensure its good stability.

It was found that when inserting into a wash basin an amount of

1 .. .3 g / 1 silicate powder which does not contain 20 ... 22% water associated with the finished product, it has only weak properties of the builder forming agent.

In fact, this silicate, in powder form, introduced into the solution, has the property to form silicon monomer conglomerates of the Si (OX) _{4 form} , where X is halogen or sodium, conglomerates which do not possess formation agent properties. Such monomer conglomerates can no longer be combined with each other to form polyanions unless the silicate concentration is at least 50 ... 500 g / 1, but in this case the association is slow.

Such concentrations (in silicate), as well as the slow kinetic kinetics (polymerization) of the monomer compounds are not compatible with the conditions and duration of the washing process specific to the washing machines.

Basically, it has been found that a powdered silicate containing 20 ... 22% chemically bound water (relative to the finished product) is recommended for detergent formulations based on silicates with 20% associated water (relative to dry silicate), obtained by spraying concentrated silicate solutions.

It has also been found that a silicate of an alkali metal rich in silicon atom of type Q ₂ and Q ₃ is capable of forming polyanionic conglomerates even at dilutions of

1 ... 3 g / 1, in a washing environment, conglomerates whose life is large enough to allow them to play the role of detergent builder.

The expression of silicon atoms in the form of Q ₂ and Q ₃ refers to the degree of association of silicon atoms between them.

Q ₂ means that each silicon atom participates in 2 -Si- O-Si- bonds, the remaining two bonds being a -Si- O -X termination, where X is an alkali metal or hydrogen.

Q ₃ shows that each silicon atom participates in three bonds - Si - O - Si the remaining bond being of the type -Si- O- X.

The forming agent according to the present invention is a solution of an alkali metal silicate, preferably sodium or potassium, which contains at least 50% of the silicon atoms in the form of Q ₂ or Q ₃ , preferably 30. ... 55% by weight of dry extracted substance, mainly sodium or potassium silicate, whose molar ratio SiO ₂ / M ₂ O may be 1.6 ... 3.5, the solution being adsorbed and / or absorbed on a chemically inert carrier with respect to silicates, preferably selected from sodium carbonate, sodium sulfate, sodium borate, sodium perborate, sodium metasilicate, polyphosphate, sodium phosphate, such as trisodium phosphate or sodium tripolyphosphate or the mixture thereof salts, the weight ratio of silicate (dry) / crystallization water of silicate being between 100/120 and 100/40.

The builder formation agenda for detergent compositions, which is the subject of the present invention, is characterized by the fact that it is composed of an alkali metal silicate, mainly sodium or potassium containing at least 30%, preferably 50% silicon atoms. Q ₂ and Q ₃ .

The silicate can have a molar ratio SiO ₂ Na ₂ O of the order 1.6-6.5, preferably 1.8-2.6.

The builder can be present in any of the solid forms (powders, granules, etc.) structured or not.

The process for obtaining the forming agent according to the present invention consists in that it is absorbed and / or absorbed by contacting a concentrated aqueous solution of an alkali metal silicate with molar ratio SiO ₂ M ₂ O of 1, 6 ... 3,5, of concentration 10 ... 60% by weight of dry matter, with an inorganic support inert with respect to silicate, the support being present in a chosen quantity such that the amount of crystallization water of silicate after adsorption and / or absorption to correspond to a weight ratio of silicate (dry matter) / crystallization water of 100/120 ... 100/140, the contacting operation is carried out by spraying at a temperature between 20 and 95 'C a of the aqueous solution based on alkali metal silicate or based on a mixture of alkali metal silicates and carbonates, on a granular support constituting a rolling bed of alkali metal carbonate particles, In a rotary granulation device, which passes at a temperature between 15 and 200'C, the speed of passage of the particles, the thickness of the layer (bed of particles) and the flow of the sprayed solution being such that the particles turn into plastic granules , by contact with other particles, the amount of silicate or silicate / carbonate mixture sprayed and the amount of carbonate-based particles being calculated so that the liquid / particle flow ratio is between 0.2 and 1 / kg, these values being expressed in sodium salts, then the granules obtained by spraying are subjected to the compaction operation, followed by the drying of the compacted granules, until a silicate-associated crystallization water content corresponding to a ratio of silicate weight (substance) / associated water between 100 is obtained. / 120 and 100/140. '

A first embodiment of the invention relates to the use of a forming agent, consisting of an aqueous solution of concentration 10 ... 60%, preferably 35 ... 50% by weight, dry matter, of an alkaline silicate, mainly sodium or potassium, having a molar ratio of SiO ₂ / M ₂ O of the order

1,6-3.5, preferably of the order of 1.8-2.6. Concentrated solution of metal silicate>

alkaline used as a forming agent is obtained, preferably, by the water solubilization of the soluble glass in the autoclave, under pressure and at temperatures of 140 * C, followed by a possible dilution; it can also be obtained by other known means, such as direct attack of sand (SiO ₂ ) with concentrated caustic soda solutions.

The obtained product was used by MRI, finding that:

- a solution containing 54% glass silicate, having a molar ratio SiO ₂ (Na ₂ O equal to 2 contains 34% species Q ₃ , 51% species Q ₂ , 12% species Qj and 3% species Q _o ;

- a 35% glassy silicate concentration solution, characterized by a molar ratio SiO ₂ (Na ₂ O of 3.5, contains 46% species Qj, 27% species Q ₂ , 16% species Q ₄ , 9% species Q, and 2% species Q _o .

The solution of the forming agent can be added by spraying on the detergent powder at the base of the tower, in the case of using a spray plant or on the mixture of ingredients of the detergent composition, in the case of dry homogenization, the amount of solution being limited by the adsorbent power of the powders. The obtained powder mixture can be moderately dry, if necessary in such a way that the dry weight ratio / associated remaining water is between 100/120 and 100/40, preferably between 100/90 and 100/50.

The amount of silicate solution is calculated so that the ratio of dry weight silica / detergent powder to be between 1/100 and 30/100, preferably of the order of 10/100 to 20/100.

Another non-limiting embodiment of the invention is the use of a>

aqueous silicate solutions containing 10 ... 60%, preferably 35 -... 50% hardened, dry extracted substance, expressed in alkali ethyl silicate, mainly sodium or potassium, whose molar ratio SiO ₂ / M ₂ It's the order

1.6 .. .3.5, preferably 1.8 ... 2.6, adsorbed and / or absorbed on a chemically inert carrier with respect to silicate, the silicate weight ratio (expressed in dry matter) / remaining water ranging from 100 / 120 to 100/40, preferably ranging from 100/90 to 100/50.

Water associated with silicate means the amount of water in the solution retained by silicate as crystallization water.

Water-soluble compounds, such as: sodium carbonate, sodium sulfate, sodium borate, sodium borate, sodium metasilicate, phosphates or polyphosphates such as trisodium phosphate, sodium tripolyphosphate, etc., may be mentioned among the inorganic supports used. , these supports being used individually or in combination.

Support generally represents

55 .. .95%, preferably 65 ... 85% by weight of the adsorbed and / or absorbed solution, expressed in dry matter (ie weight of solution expressed in dry substance + weight of support).

The so-called adsorbed / or absorbed solution can be prepared by adsorption and / or absorption of a concentrated silicate solution of an alkali metal whose molar ratio SiO ₂ / M ₂ O is of the order of 1,6 ... 3,5, of preferably 1.8 ... 2.6, having a concentration in dry matter extracted of 10 ... 60%, preferably 35 ... 50%, on an inorganic support inert with respect to silicate, the amount of support thus being calculated that the amount of water remaining associated with the silicate after adsorption and / or absorption corresponds to a weight ratio of silicate (expressed in dry matter) / water associated with silicate of the order of 100/120 to 100/40, preferably from 100 / 90 to 100/50.

Absorption and / or adsorption can be achieved by adding, in particular spray, the concentrated silicate solution on the organic substrate, in a known LODIGERR type mixer or in a granulation device (drum, tray ...), at a contained temperature. between 20 and 95 ^C C, preferably 70 ... 95 ° C.

The inorganic supports used are those mentioned in the list below.

The amount and concentration of the silicate solution is dependent on the absorbing and / or adsorbing power of the support, taking into account the possible possibility of the support to form crystalline hydrates; the amount of water not associated with the silicate in the form of hydrate in the support can be determined by known methods, that is, by thermo-differential analysis or X-ray diffraction.

The retained water, possibly, of support in a form other than the mentioned hydrates can be determined by physico-chemical methods (thermoporosity, thermogravimetry, NMR, IR).

The limit of the absorbent and / or adsorbent power of the support can be determined according to known methods, for example by measuring the variation of the angle from the base of the slope of the flow, depending on the amount of silicate solution added.

If necessary, the mixture consisting of the support and the silicate solution can be dried, but in such a way as to obtain the desired proportions of water associated with the silicate.

The particles (of the silicate solution adsorbed and / or absorbed on the substrate) can be ground, if desired, to obtain particles with an average diameter of

200 ... 800 u.

The products obtained by adsorption and / or adsorption of the solution of alkali metal silicate on alkali metal carbonate, in the form of spherical cogranules, are the subject of the present invention, constituting builder training agents.

Spherical cogranules of hydrated silicates of alkali metals adsorbed and / or absorbed on carbonates of alkali metals can be prepared by a process characterized by the following phases:

- the aqueous solution of the alkali metal silicate as such or a mixture of alkali metal silicates and carbonates is sprayed on a movable (rolling) bed of alkali metal carbonate particles, located in a rotary granulation device, the bed displacement speed , the thickness of the alkaline carbonate layer and the flow rate of the sprayed solution are calculated so that each particle is transformed into a plastic cogranule in contact with other particles;

- the cogranules obtained are densified (compaction);

- the densified cogranules are dried until a water content associated with the silicate is obtained, corresponding to a dry weight / water weight ratio of 100 / 120-100 / 40.

Among the silicates and carbonates of alkali metals, those of sodium and potassium may be mentioned, but mainly those of sodium.

The aqueous solution based on silicate or sprayed silicate / carbonate mixture may have a content in dry extracted substance of 30 ... 55% by weight, preferably

30 .. .54% by weight: the alkali metal silicate has a molar ratio SiO ₂ / M ₂ O of

1.6 .. .3.5, preferably 1,8-2,6 and, in particular, around 2; the carbonate may be present in proportions corresponding to the desired finished product.

Spraying the silicate solution or the silicate / carbonate mixture is carried out at a temperature ranging from 20 to 95 ° C, preferably 70 ... 95 ° C; spraying can be improved by simultaneous introduction (for example, by means of a bifluid nozzle) of pressurized air at spray temperature.

The particles used to make the cogranules are mainly made of carbonate of an alkali metal having the following characteristics:

- average diameter of 10 ... 150 u, preferably 20 ... 100 u and, in particular, 30 ... 80 u;

- unsaturated (volumetric) filling density: of the order of 0.1 ... 1.1 g / cm ³ , preferably 0.6 ... 1.1 g / cm ³ ;

- water content: 0,05 ... 0,4%, preferably 0,1 ... 0,3% by weight;

- insoluble matter content:

5 ... 100 mg / kg, mainly 10-60 mg / kg.

Grinded or not carbonates can be used. Along with carbonates, antimicrobial polymers (carboxymethylcellulose), enzymes, commonly used in detergent receptacles with a particle diameter and volumetric density close to that of carbonate can be used (in concentration less than 100% by weight of cogranules).

The device used to perform the cogranulation operation by spraying refers to any rotary device (rotary drum, mixer, granulator, dripping turbine, rotary tray).

A first preferred way to obtain these cogranules is to use a rotary granulator, which allows the particles to pass through the thin layer. The derailleur devices (turbines), which have an axis of rotation inclined with respect to the horizontal under an angle greater than 20 °, preferably greater than 40 °, are the most indicated: their geometry may be different: truncated, flat, in scale or a combination of these three forms.

A second way of obtaining the cogranules consists of the use of a rotary drum, whose angle of inclination is at least 30 °, preferably 50 °. The carbonate particles pass at a temperature of 15 ... 200 ° C, preferably 15 ... 120 ° C and, in particular, 15-30 ° C. The quantities of silicate solution or silicate / carbonate mixture to be sprayed and the inorganic support are calculated so that the liquid / particle flow ratio varies from 0.2 to 0.8 1 / kg, preferably 0.4. ..0,7 1 / kg and, in particular,

0.662 ... 0.7 1 / kg, these values being related to sodium salts.

The flow rate of the spray solution, the rate of passage of the particles, as well as the thickness of the particle layer are chosen so that each particle absorbs liquid and agglomerates other particles with which it comes in contact, finally obtaining plastic granules '' and not a paste. .

The velocity of passage of the particles and the thickness of the layer is regulated by the flow rate of insertion of the particles in the granulation device and by the constructive characteristics of the latter.

The settling time of the particles in the drum or tray granulation device is generally 15-40 min.

It is up to the specialist to choose, depending on the raw material, to opt for one device or another, depending on the quality of the desired finished product. The following features of the device will be taken into account:

- geometry: truncated, flat, in scale or combination of the three forms;

- dimensions: depth, diameter;

- the inclination angle;

- rotation speed;

- relative positions of solids and liquids supply; when using a turbine device for dredging. When using a drum device, account shall be taken of:

- geometry (tube diameter);

- the inclination angle;

- rotation speed;

- tube loading;

- relative position of feed of solids and liquids.

The raw cogranules obtained (non-woven and unscrewed) have different characteristics depending on the working conditions. They are generally characterized by:

- silicate content of 7 ... 30% by weight, preferably 11 ... 23% by weight and in particular 21 ... 23% by weight;

- water content of 18 ... 20% by weight, preferably 25 ... 29% by weight, and in particular 27 ... 29% by weight.

The densification operation can be performed at ambient temperature by passing the cogranules obtained during the granulation step through a device. This device is preferably other than the granulation device. This densification step can be advantageously achieved by introducing and maturing the cogranules in a rotary device. The inclination angle of the drum is at least 30 °, preferably at least 50 °. The dimensions of the drum, the speed of rotation and the ripening time of the cogranules are chosen according to the investigated density (desired); The ripening times are generally variable from 20 min to 3 h, preferably from 20 to 90 min.

The mixers.granuladoras are equally well used for the operation of achieving the desired density.

The desired density and cogranulation operations can also be carried out in the same device, for example in a device for scaling, the desired density being achieved by passing (running) the cogranules through the last area of the apparatus. Also, the two operations can be performed in a drum with two sections.

The dense (compact) cogranules are then dried by any known means. The most effective method is the fluidized bed drying with an air flow, at a temperature of 40 ... 90 ° C, preferably

60 .. .80 ° C. This operation is conditioned by the temperature of the air, the initial water content of the cogranules, the water content of the dried cogranules, as well as the fluidization (flow) conditions; the specialist knows to adapt these conditions according to the quality of the product being researched.

The dense (compact) dried cogranules are generally characterized by:

- silicate content of the order

8 .. .38% by weight, preferably 14 ... 31% by weight and, in particular, of the order 24 ... 31% by weight;

- carbonate content of the order of 4787% by weight, preferably 59-81% by weight, and in particular 64-69% by weight;

- water content of 5-25% by weight, preferably 7-20% by weight and, in particular, 12-20% by weight:

- unmatched volumetric density 0.7-

1.5 g / cm ³ , preferably 0.75-1.5 g / cm ³ and, in particular, 0.8-1 g / cm ³ ;

- mean diameter of the order of 0.4 to 1.8 mm, preferably 0.6-0.8 mm, with a deviation of 0.02 to 0.3 tiplO _lo, preferably 0.05 to 0.1.

These cogranulating / densifying (compacting) drying stages allow the production of hydrogel silicate cogranules of metals and carbonates of perfectly spherical, dense (compact) alkaline metals that dissolve rapidly in water.

Spherical cogranules based on hydrated sodium silicate and sodium carbonate are the most recommended for the preparation of detergent compositions for dishwashers and washing machines, their basic characteristics being:

- silicate content: 24-32% by weight;

- carbonate content: 64-69% by weight;

- water content: 12-20% by weight;

- unadjusted volumetric density: 0.7-

1.5 g / cm ³ , preferably 0.8 - 1 g / cm ³ ;

- dissolution rate in water, 90% concentration is less than 2 min, and 95% concentration is less than 4 min;

- average diameter is 0.4 - 0.8 mm with a 10g ₁₀ deviation of 0.05 - 0.1.

The dissolution rate at concentrations of 90% and 95% in water means the time required for dissolving the product of concentration 90% and 95% in water at 20 ° C, the final concentration of the solution being 35 g / 1.

The dishwashing detergent compositions obtained according to the invention contain 3 to 90% by weight, preferably 3 to 70% by weight of the builder, and the detergent compositions for the washing, contain 3 to 60% by weight, preferably 3 to at 40% by weight of the builder training agent (these quantities are expressed by the dry bulk content in relation to the weight of the composition).

Along with the builder agent, which is the subject of the present invention, there is at least one surfactant in the detergent composition in the amount which can range from 8 to 20%, preferably from 10 to 15% by weight, compared to the given composition.

Among the surfactants we can mention:

- soap anionic surfactants such as alkali metals (alkaline salts of C ₈ C ₂₄ alkyl fatty acids alkali sulphonates (C ₈ - C ₁₃ alkylbenzene sulphonates, C ₁₂ -C ₁₆ alkyl alcohol sulfonates) , ethoxylated and sulfated fatty alcohols with C ₆ -C ₁₆ alkyl chain, ethoxylated and sulfated alkylphenols where alkyl is C ₈ -C ₁₃ alkaline sulfosuccinates (C ₂ -C ₁₆ alkylsulfosuccinate);

- nonionic surfactants such as polyethoxylated alkylphenols, where C ₆ C ₁₂ alkyl, ethoxylated aliphatic alcohols with C ₈ -C ₂₂ alkyl chain, ethoxylated / propoxylated copolymer block, polyethoxylated amides;

- the surfactants active amphotopes of the type alkylbenes;

- cationic surfactants such as alkyltrimethylammonium chloride or bromine or alkyldimethyl ethyl ammonium.

Other ingredients that may be present in detergent compositions:

- type builder training agents:

- phosphates in a concentration of less than 25% of the total weight of the detergent formulation;

- zeolites up to about 80% of the total weight of the detergent formulation;

- nitriloacetic acid up to about 10% of the total weight of the formulation;

- citric acid, tartaric acid up to approx. 20% of the total weight of the formulation, the total amount of builder being around 0.2 to 80%, preferably from 20 to 45% of the total weight of the detergent composition;

- bleaching agents such as perborates, percarbonates, chloroisocyanates, Ν, Ν, Ν ', Ν' - tetraacetylethylenediamine (TAED) up to about 30% of the total weight of the detergent composition;

- copolymer antifouling agents of acrylic acid and maleic anhydride in quantities up to 10% of the total weight of the detergent composition;

- anti-delivery agents such as carboxymethylcellulose, methylcellulose in an amount that can reach approx. 5% of the total weight;

- Sodium sulphate support for powdered detergents, in concentrations that can reach 50% of the total weight of the detergent composition.

The following are eighty embodiments for illustrating the invention:

Examples 1 ... 5. Performance builder type

- sodium silicate solution with SiOj / Na ^ - molar ratio? concentration 45% by weight of dry extracted substance (example

2);

- sodium silicate solution, SiO ₂ / Na molar ratio, O = 3.4, concentration 35% by weight of dry extracted substance (example

4) were measured with a TERGOMETER (US Testing Company, Hoboken, USA) in binary mixture with an anionic surfactant - LABS (ALDRICH sodium dodecylbenzenesulfonate). The reflectance was determined using the GARDNER reflectometer.

These values (performances) were compared with those of the standard products:

- LABS - solution 2 g / 1 (example 1);

- atomized silicate powder having a SiO ₂ / M ₂ O ratio of 2, containing 22% water (or 28.2% water relative to dry silicate) (example 3);

- atomized silicate powder with a ratio equal to 3.4 water content 18.6% (or 22.8% water relative to dry silicate) (example 5). The measurements were performed for silicate solutions of concentration 4 g / 1.

The results of these measurements are presented in Table 1

Table 1

Example Detergent (washing power) on Cotton EMPA PEC EMPA Cotton VI cumulative LABS 2'g / l 17,26 10.53 17.28 45.07 LABS 2 ² g / IR ² sol, 4 g / 1 19.53 21.61 20.48 61,62 LABS 2 ³ g / 1 R2 atomized 4 g / 1 20.23 20.93 18.44 59.60 LABS 2 ⁴ g / 1 R3.4 mol.4 g / 1 21.03 21.29 20.09 62.41 LABS 2 ⁵ g / l atomized R3.4 4 g / 1 21.69 18.69 20:28 60.86

Method of determination. Principle: 10 A car wash is simulated in a thermometer, introducing normal dirty tissue samples and washing at 65 'C with surfactant and builder. The washing takes 30 minutes. Measure 15 the color of the fabric before and after washing. A blank sample is washed only with the surfactant, to be able to evaluate the performance of the tested builder.

Working method: 20

The thermometer is an apparatus consisting of 4 stainless steel vessels, on which pulsators are adjusted which can be adjusted to 100 cycles per minute. The vessels are placed in a pan with water thermostated at 65 ° C. 25

1) 11 hard tap water (34 'TH French) is introduced into each vessel. When the water has reached the temperature in the tank it is introduced:

- 5 samples 10 x 12 cm of type cotton

405 W from TEST FABRIC; 30

- 5 samples 10 x 12 cm polyester-cotton (PEC) with reference number 7435 from the company TEST FABRIC;

- 2 samples 10 x 12 cm dirty cotton EMPA (35 China ink and olive oil mixture), article 101 of GALLEN;

- 2 samples 10 x 12 dirty cotton with red wine - article 114 of the company GALLEN;

- 2 samples 10 x 12 cm polyester- 40 cotton (PEC) soiled EMPA article 104 from GALLEN company.

2) The following three operations are performed simultaneously:

- timekeeping is triggered;

- agitation begins;

- add the builder / surfactant formation agent mixture.

The builder agenda is tested at a concentration of 4 g / 1 (calculated quantity in dry product) and 2 g / 1 LABS is added.

3) Rinse:

After passing the 20 min. wash, discard the wash water, rinse the fabric three times with one liter of cold water from the tap.

4) Squeezing and drying:

The specimens are crumpled, pricked, individually spread on absorbent paper. The fabrics are then passed twice in a dryer (photo type between two sheets of absorbent paper at a temperature of 110 ° C).

5) Color measurement:

Calibrate the GARDNER device at the zero position, using a black plate, specific for this purpose, then read the values L, a, b, for a normal white plate of the same type as the black plate.

It places the color in the white or black area.

L = 100 corresponds to the white sample

L = O corresponds to the black sample a locates the color in the green or red domain a> A color tends to the red a <A color tends to the green b b places the color in the yellow or blue domain b> A color tends to yellow b <A color tends to blue After calibration, the actual measurements are made. Two samples from each category of fabric are taken from the vessel, 5 measurements are made on each sample (ie, one at the center and 4 at the corners) by placing a heavy metal plate on the fabric, then the arithmetic mean of the 10 determinations is made. It is done in the same way as the non-washed fabrics.

6) Interpretation of results:

Calculate DL and DE for each determination and each type of fabric.

DL = L (washing soup) - L (before washing)

Yes = a (before washing) - a (after washing)

Db = b (before washing) - b (after washing)

DE = DL ² + Yes ² + Db ² = Detergency (washing power).

The average DL and DE parameters are calculated for each product and each type of dirty fabric.

>

Then, for each product is calculated:

Det (ergence) EMPA cotton = DE average EMPA cotton

Det (emergency) PEC EMPA = OF average PEC EMPA

Det (ergence) cotton VIN = DE medium cotton VIN

Cumulative det (ergence) = Sum of detergents of cotton EMPA, PEC, EMPA cotton VIN.

Examples 6 and 7. Introduce in a LODIGE M5G mixer (marketed by LODIGE company) 800 g of anhydrous tripolyphosphate H ₂ ^e , marketed by

Rhone-Poulenc.

After sealing and stirring start (speed 400 rpm), spray 200 g of sodium silicate solution, molar ratio SiO2 / Na2O = 2, concentration 45% dry extracted substance. This addition takes 10 min; the mixture is further stirred for a further 10 minutes, the product is left for 2 hours to stabilize, on a platter, in liuber air and at room temperature.

The characteristics of the product are as follows:

- Partially hydrated TPP: 82% by weight;

- sodium silicate: 9% by weight;

- water associated with silicate: 9% by weight, or 100% in relation to dry silicate.

The amount of total water contained in the product is determined, determining its weight loss by heating to 500 ° C; on the other hand, the amount of water fixed in the form of hydrate is determined by thermodynamic analysis. The amount of associated water is calculated by the difference between the total water and the water fixed in the form of hydrate.

- average diameter = 250 microns.

The performances of the builder of this type are determined according to the method described above, at the same time replacing the two samples PEC soiled EMPA article 104 by two samples of soiled cotton WEK from KREFELD, of the same size (example 6).

These performances are then compared to those corresponding to a mixture of anhydrous TPP powder type H ₂ ^R and atomized silicate with molar ratio SiOj / NajO = 2, concentration in water 22%, the weight ratio TPP / dry silicate being 800/90. The working conditions are the same (fleet concentration 4 g / 1) (example 7).

The results of the determinations are presented in table 2.

Table 2

Name of fabric Detergency (washing power) Example 6 7 LABS 2 g / 1 LABS 2 g / 1 R2 only. condit. TPP 4 g / 1 Atomized R2 + TPP 4 g / 1 White cotton -0.20 0.06 KREFELD cotton 14,15 13.47 Cotton EMPA 25.14 25.42 Cotton VI 19.67 18.77 Det. cumulated 58.96 57.66

Example 8. The granulation system 10 consists of a plate (flat tray) with a diameter of 800 mm and a depth of 100 mm. During the granulation, the speed of rotation is 35 rpm and the inclination of the axis of rotation with respect to the horizontal is 55 '. 15 The granulation tray is continuously fed (about 21.4 kg / h) with powder consisting of fine sodium carbonate particles whose characteristics are as follows:

- alkalinity content: 99.61%; 20

- water content (by weight): 0,12%;

- unpaired volumetric density = 0.56 g / cm ³ ;

- average diameter = 95 microns; 25

- insoluble = 58 mg / kg.

This powder is sprayed with a bifluid nozzle of air, at a temperature of 80 ° C, of sodium silicate solution; spray rate is 13.4 30 1 / h, solution temperature 80 'C; the bifluid nozzle is located at a distance of 20 cm from the base of the dripping turbine. The concentration of the active substance and the molar ratio SiO / Na ^ of the solution to be sprayed is 43% (by weight), 35 respectively 2. during the spraying, the plate (plate) which is the powder rotates.

The average settling time of the particles on the plate is approx. 10 - 15 min.

The temperature of the particles at the exit of the plate is ambient temperature.

The granules removed from the plate are inserted in a circular tube with polished walls, diameter 500 mm, length 1300 mm and which has a slope of 50 '. The outlet (output) aperture is adjusted in such a way that the average settling time of a particle is around 40 mm. The rotational speed of the drum (18 rpm) is chosen so that the rolling particle bed is continuous, which favors the densification (compacting) of the particles.

The granules thus obtained are dried on a fluidized bed at 80 'C (the temperature of the fluidizing air is 85 ... 90' C), for 10 ... 15 min.

The dry product has the following characteristics:

- carbonate content (by weight): 65%;

- silicate content (by weight): 21% ± 0,5%;

- water content (weighted): 13,5%

- unadjusted volumetric density: 0.90 g / cm ³ ;

-% refutation at 1 mm (by weight): 10.8%;

- average diameter:

0.73 mm;

-%, by weight passing to 0.2 mm: 6%;

- 90% (by weight) of the product is dissolved in 50 s (aqueous solution concentration 35 g / 1 at 20'C);

- 95% (by weight) of the product is dissolved in 65 s (aqueous solution concentration 35 g / 1, at 20 'C);

- white L degree: 96.3;

- wear resistance: 7%.

The granules exhibit excellent storage behavior.

Measurement of wear resistance

A fluorometer is used, a device normally used to characterize hydraulic binders and described in French standards P 15-443.

Procedure:

50 g of product is sieved using a laboratory site ΝΟΤΟ - LAB (marketed by PROLABO) with a granulation between 1200 and 180 microns.

The part between 180 and 1200 microns is recovered.

Weigh, with approximate accuracy, 25 g of test product; note with M the exact quantity weighed.

Place the product in the fluorometer. Weigh an empty and dry Soxlhet filter (marketed by PROLABO) and place it at the top of the fluidization tube; note the mass of the filter with Mj. Fluidize for 5 minutes (dry air flow: 15 l / min).

The product is recovered in the form of fine particles, which were deposited, possibly, on the vertical walls and the fluidization tube, with the help of a brush of adapted diameter. It weighs. The mass of these recovered particles and the filter is noted with M ₂ . The residue remaining at the base of the fluidization tube is sieved again through the ROTO-LAB sieve and the fine particles with a diameter of less than 180 microns are recovered. The recovered quantity is also weighed. The mass of these particles is noted as M ₃ .

calculation:

The percentage of particle wear is equal to the percentage of fine particles with a diameter of less than 180 microns, formed during fluidization of the product.

(Af ₃ + M ₂ - x 100% wear = ---------------------- M

Example 9. Repeat the operations described in example 1, with the following changes:

Cancellation phase:

- platter (granulator plate): Rotation speed will be 30 rpm <7min;

- powder feed rate: 22 kg / h;

- feed flow of silicate solution: 13 1 / h;

Densification phase (compaction):

- rotation speed of the drum: 10 i

rev / min;

Drying phase in fluidized bed:

- temperature: 90'C;

- time: 20 min.

The dry 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%;

- unpaired volumetric density = 0.86 g / cm ³ ;

- refusal at 1 mm,% by weight = 2.6%;

- average diameter = 0.64 mm;

-%, by weight passing to 0.2 mm = 7.3%;

- 90% (by weight) of the product is dissolved in 75 s (aqueous solution containing 35 g / 1 at 20 ° C);

- 95% (by weight) of the product is dissolved in 102 s (aqueous solution containing 35 g / 1 product at 20 ° C);

- white L = 95.6;

- wear resistance: 9.2%.

The granules have excellent storage stability.

Example 10. The granulation system consists of a drum with a rotational speed of 40 rpm, polished walls with a diameter of 500 mm, a length of 1300 mm and an inclination of the axis to a horizontal of 7.5%. The discharge aperture is adjusted so that the average settling time of a particle is 15 ... 20 min.

The drum is fed at a rate of 37 kg / h with carbonate powder, having the characteristics presented in examples 1 and

2. This powder, which is in rotational motion, is sprayed with a bifluid nozzle, with air at a temperature of 80'C silicate solution (containing 45% by weight of active substance and a ratio: SiOj / NazO equal to 2), at a temperature of 80'C and a flow rate of 10 1 / h. The bifluid nozzle has a flat jet and is located in the first third of the drum.

The cogranules have an ambient temperature at the exit of the drum and have a density of 0.68 g / cm ³ .

The cogranules are then subjected to the operation of discontinuous densification for one hour in a rotary drum with polished walls, diameter 500 mm, length 1300 mm and which have an axis inclination to the horizontal 5 '. The rotational speed of the drum is 20 rpm.

The granules thus obtained are dried on a fluidized bed at a temperature of 65 'C (the temperature of the fluidizing air being 70' C), for a drying time of 15 minutes.

The dry product has the following characteristics:

- carbonate content (by weight) = 62%;

- silicate content (by weight) = 20,5 ± 0,5%; '

- water content (by weight) = 17.6%;

- unpaired volumetric density = 0.820;

-% refusal by weight at 1 mm = 5%;

- average diameter = 0.65 mm;

- 90% (weighted) product is dissolved in 50 s (aqueous solution containing 35 g / 1 product at 20 ° C;

- 95% (by weight) of the product is dissolved in 63 s (aqueous solution containing 35 g / 1 product at 20 ° C).

The granules have excellent storage stability.

Example 11. Repeat the operations described in example 3, with the following changes:

Densification operation:

- discontinued for 2 hours.

The dry product has the following characteristics:

- carbonate content (by weight) = 60.8%;

- silicate content (by weight) = 19.3% ± 0.5%;

- water content (by weight) = 19.19%;

- unpaired volumetric density = 0.91 g / cm ³ ;

-% by weight refusal at 1 mm = 1.6%;

- average diameter 0.57 mm;

-% by weight passing to 0.2 mm = 1.22%;

- 90% (weighted) product is dissolved in 45 s (aqueous solution containing 35 g / 1 at 20 _t C);

- 95% (by weight) of the product is dissolved in 45 s (aqueous solution containing 35 g / 1 at 20 ° C).

The granules have excellent storage stability.

Examples 12 and 13. The performances of the builder agent of the cogranules obtained according to example 8 are measured according to the method described in examples 1 ... 5. They are compared with those corresponding to a mixture of sodium carbonate-powder and atomized sodium-silicate-silicate, with a ratio SiO ₂ / NazO = 2 containing 22% water in the finished product (ie 28.2% water relative to dry silicate ), the carbonate / silicate weight ratio is 3/1 (carbonate / atomized Rj).

The results are presented in the table

3. The quantities of carbonate and silicate shown in the table are expressed in dry matter. It is found that the performance of the cogranules of the builder is superior to those corresponding to the carbonate / silicate mixture.

Example 14. Prepare in a LODIGE M5G mixer, according to the working method of Examples 6 and 7, particles starting from:

- 1800 g of sodium carbonate - powder, the average particle diameter being 110 microns;

- 1200 g of sodium silicate solution, SiO ₂ / NazO molar ratio equal to 3.4 and a content of 37% dry extracted substance.

News

After 5 minutes after the addition of the silicate solution, a further 5 minutes is homogenized, after which it is left to ripen for 2 hours at ambient temperature; the product having the following characteristics is recovered: 5

- Sodium carbonate: 60% by weight;

- Sodium silicate: 20% by weight;

- water associated with silicate = 20% by weight (or 100% relative to dry silicate);

- average diameter: 400 microns.

This product is introduced into a mixture of dry ingredients, finally obtaining a detergent composition, as follows:

Detergent composition Weight parts%%

- linear alkylbenzene sulphonate25

- CEMULSOL OF 618 ^R 3

- CEMULSOL LA 90 ^R 2 (surfactant agent of SFOS company)

- zeolite 4A18

- product according to example no.425.8

- SOKALAN CP ₅ ^R 4.0 (BASF copolymer)

- carboxymethylcellulose 1.5

- TINOPAL DMSX0,2

- TIMOPAL SOP0.2 (CIBA-GEIGY launcher)

- ESPERASE ^r (enzymes from NEW) 0.3

- RHODORSIL 20444 ^R 2.0 (Rhone-Poulenc antifoam)

- sodium perborate, 4 H ₂ O15.0

- TAED3.0 jzH sol.10 g / 1 is 10.25

The test for determining the washing power 30 was performed on a POM 71 ^R washing machine from WASCATOR.

The test conditions are as follows:

- washing cycle: 60 C; 35

- total duration of the cycle: 70 min, without pre-washing;

- number of cycles: 3 per wash;

- water hardness: 32 degrees HT French; 40

- quantity of clothes: 3.5 kg white cotton cloth;

- the fabrics tested:

- gray cotton: Test-Fabric,

KREFELD 10 C, IEC 106, EMPA 101; 45

- gray polyester / cotton: TestFabric, KREFELD 20 C, EMPA 104;

- protein stains: blood (EMPA 111), cocoa (EMPA 112), mixed (EMPA 116);

- oxidizable stains: tea (KREFELD 10 G), organic cotton (EMPA 222), VIN (EMPA 114);

- washing doses:

- first series 5 g / 1 or 5 x 20 = 100 g / wash;

- the second series: 8 g / 1 or 8 x 20 = 160 g / wash.

Method of measuring the dirt and stain washer

Photometric measurements (measure the amount of light reflected by the fabric) allow the percentage of dirt removal to be calculated. An ELREPHO 2000 device from DATACALOR is used.

The elimination of dirt is expressed by the formula:

% Elimination = ——— x 100 A-B where A = reflection of blank cotton blank;

B = reflectance of the dirty witness; 5

C - reflective of dirty fabric »» after washing.

The reflections are determined with the help of the trichrome blue component, without the action of the optical bleachers. 10

Number of measurements per sample = 4.

Number of samples washed: 2.

Number of washes: 3

Let 4 x 2 x 3 = 24 measure the dirt, on 15 products and on the studied concentration.

The anti-fouling test in the washing machine was performed using a SCHULTESESS SUPER 6 DE LUXE ^R drum machine. 20

The test conditions are as follows:

- cycle used: 60'C;

- total cycle time: 65 min, without pre-washing;

- number of cycles: 25 accumulated washes;

- water hardness: 21.2 degrees HT French;

- test fabric used: control strip, characterized according to NFT 73,600;

- quantity of laundry: 3 kg 100% cotton fluffy towels;

- washing dose: 5 g / 1.

Dry the specimens that were subjected to 25 washes; they are weighed and calcined at 900 'C. The ash content and percentage are calcined with respect to the initial weight of the specimens. The results of the different tests are presented in table 3.

Table 3

Textile Washing power (detergent) Example 12 Example 13 LABS 2 g / 1 cogranule 4 g / 1 LABS 2 g / carbonate 3 g / 1 R ₂ atomized 1 g / 1 Cotton EMPA 19.27 17.63 PEC EMPA 24.52 23.13 Cotton VI 19.29 19.49 Cumulative detergent 62.99 60.24

Example 15. A detergent composition, analogous to that of Example 14, is prepared by replacing the Builder mixture: zeolite 4A + SOKALAN builder; - zeolite 4A 30 parts; - R ₂ atomized silicate 3 parts; - light carbonate 6 parts; - Sodium sulphate 4.8 parts; - SOKALAN CP5 4.0 parts

produced from example 14 + CP5, with the following mixture

The test results regarding the degree of removal of the dirt and the degree of anti-fouling are presented in table 4.

30

Table 4

Example 14 15 Cotton detergent 5 g / l 57.7 50.5 Cotton detergent 8 g / l 62.5 56.2 PEC detergent 5 g / l 38.4 36.6 PEC detergent 8 g / l 46.7 44.5 Protein detergent 5 g / l 42.6 46.6 Protein detergent 8 g / l 50.8 54.1 bleaching 5g / l 43.9 37.3 bleaching 8 g / l 57.9 45.3 incrustation 5 g / l 0.69 0 .85 Overall average 5 g / l 45.65 42,75 Overall average «Ort 54 47 50 07.

Examples 16 ... 18. The product of Example 15 is introduced into the mixture, in a LODIGE M5G ^R appliance, with specific ingredients, to obtain a detergent composition for dishwashers. These compositions are shown in Table 20

These compositions were tested in a MIELE ^r household dishwasher, whose water softener was not regenerated; for this reason he will supply 25 limestone water, which has a total hardness of 3O'TH French. With each composition, used at a concentration of 3 g / l, 10 'washes are accumulated on soda-glass plates, initially perfectly clean. 30

The plates are then subjected to photometric measurement using the apparatus

GARDNER, identical to the one used in Examples 1 ... 5. The total amount of light L retransmitted from the sample is measured. If L is between 7 and 14, the bottle is considered to be slightly matted. If L is between 4 and 7, the result is considered very good, the glass being clear (completely transparent).

The product of Example 8 is comparable in performance with a mixture of sodium carbonate cogranules and BRITSIL H20 ^R cogranules (SiO / Na ^ = 2 ratio and containing 20% water, marketed by Philadelphia Quartz).

The results are presented in the table

Example 15 16 17 Cogranule 59 54 - Sodium carbonate cogranulated - - 31 BRITSIL H 2 o ^R - - 17 Sodium citrate 17 20 25 Sodium polyacrylate Mw = 4500 4 5 5 Sodium sulphate 4 5 Non-ionic surface agents 2 2 6 Sodium perborate, 1H ₂ O 10 10 10 TAED 2 2 2 enzymes 2 2 2 IT 5.3 5.2 5.2

It is found that the use of cogranules from Example 8 allows the reduction of the amount of sodium citrate (expensive) and polyacrylate (non-biodegradable).

Claims (15)

claims 1. Forming-builder-agent for detergent compositions based on alkali metal silicates, characterized in that it consists of a solution of an alkali metal silicate, preferably of sodium or potassium, containing at least 50% atoms. of silicon in the form of Q ₂ or Q ₃ , preferably 30 ... 55% by weight of dry extracted substance, mainly sodium or potassium silicate, whose molar ratio SiO ₂ / M ₂ O may be 1.6 ... 3.5, the solution being adsorbed and / or absorbed on a chemically inert carrier against silicates, preferably selected from sodium carbonate, sodium borate, sodium perborate, sodium sulfate, sodium metasilicate, phosphate or polyphosphate, such as trisodium phosphate or sodium tripolyphosphate or the mixture of these salts, the weight ratio of silicate (dry) / crystallization water of silicate being between 100/120 and 100/40. 2. Former-builder-agent for detergent compositions, based on alkali metal silicates, according to claim 1, characterized in that the chemical inert support is in the proportion of 55 ... 95% by weight of dry matter, relative to the mixture. 3. Forming-builder-agent for detergent compositions, based on alkali metal silicates, according to claims 1 and 2, characterized in that it is in the form of spherical granules based on alkali silicates and carbonates, the granules in the dry and compacted state. having: 8 ... 38% by weight silicate content (SiO ₂ / M ₂ O ratio between 1.6 and 3.5); 47 ... 87% by weight carbonate content; 5 ... 25% by weight water content; density not found between 0.7 and 1.5 g / cm ³ ; average diameter between 0.4 and 1.8 mm, with a 10g ₁₀ deviation of 0.02 ... 0.3. 4. Forming agent-builder- for detergent compositions according to claims 1 ... 3, characterized in that, in the case of spherical granules of hydrated sodium silicate and sodium carbonate, compacted and dried, the characteristics are: 24 .. .31% by weight content of sodium silicate (molar ratio SiO ₂ / M ₂ O being 1.2 .. .2.6); 12 ... 20% by weight water content; 64 ... 69% by weight sodium carbonate content; density not found between 0.7 and 1.5 g / cm ³ ; average diameter of 0.4 ... 0.8 mm, with a log ₁₀ deviation of 0.05 ... 0.1, the dissolution rate in water at 90% concentration of maximum 2 min, and at the concentration of 95 % below 4 min. 5. Forming agent-builder for detergent compositions according to claims 1 ... 4, characterized in that, incorporated in powdered detergent compositions for dishwashers, it provides a content of 3 ... 90% in dry silicate weight in relation to the composition. 6. Builder forming agent for detergent compositions, according to claims 1 ... 4, characterized in that, incorporated in powdered detergent compositions for fabric washing machines, it provides a content of 3 ... 60% by weight silicate dry relative to the composition. 7. Builder forming agent for detergent compositions, according to claims 1 ... 6, characterized in that it is used as a detergent composition forming agent in the form of an aqueous solution of an alkali metal silicate, having a concentration between 10 and 60%. by weight dry matter, with a molar ratio SiO ₂ / M ₂ O between 1.6 and 3.5 and containing less than 50% silicon atoms in the form of Q ₂ and Q ₃ . 8. Process for obtaining the forming-builder for detergent compositions, based on alkali metal silicates, characterized in that it is absorbed and / or absorbed, by contacting a concentrated aqueous solution, of an alkali metal silicate with molar ratio SiO ₂ / M ₂ O of 1.6 .... 3.5, of concentration 10 .. .60% by weight of dry matter, with an inorganic support inert with respect to silicate, the support being present in a chosen amount such that the amount of crystallization water of the silicate after adsorption and / or absorption corresponds to a weight ratio. silicate (dry substance) / crystallization water of 100/120 ,,, 100/140, the contacting operation is carried out by spraying at a temperature between 20 and 95'C of 5 aqueous solution based on alkaline metal silicates or based on a mixture of silicates and carbonates of alkali metals, on a granular support, which constitutes a rolling bed of particles based on carbonates of 10 alkaline metals, located in a rotary granulation device, through which a temperature is passed between 15 and 200'C, the speed of passage of the particles, the thickness of the layer (the bed of particles) and the flow of the spray solution 15 being chosen so that the particles are transformed me in plastic granules, by contact with other particles, the amount of silicate or silicate / carbonate mixture sprayed and the amount of carbonate-based particles 20 being calculated so that the liquid-to-particle flow ratio is between 0.2 and 0 , 8 1 / kg, these values being expressed in sodium salts, then the granules obtained by spraying are subjected to the compacting operation, after which the compacted granules are dried, until a crystallization water content associated with the silicate is obtained, corresponding to a weight ratio. silicate (dry matter) / water 30 associated between 100/120 and 100/140. 9. Process according to claim 8, characterized in that a rolling bed, consisting of carbonate particles 35 of an alkali metal, is used in the spraying operation, having the characteristics: average diameter 10 ... 150 μιη, density volumetric in unsaturated state of 0,4 ... 1,1 g / cm ³ , contained in water of 0,05 ... 0,4%, contained in insoluble substances of 5 ... 100 40 ♦ 9 mg / kg . 10. Process according to claims 8 and 9, characterized in that the rolling bed consists of particles containing at least 10% by weight granules of a nature other than alkali metal carbonate and having a diameter and density similar to granules only on the basis of alkali metal carbonate. Process according to claim 8, characterized in that the rotary granulation device through which the rolling bed of alkali metal carbonate particles is a rotary granulator, which allows the particle to pass in a thin state and which may be a dripping turbine or a drum. Process according to claim 8, characterized in that the compaction operation for increasing the density of the granules obtained in the granulation phase is carried out at ambient temperature, by passing these granules through a rotary device, which can be a rotary drum. Process according to claim 8, characterized in that the granules obtained after compaction are dried in a fluidized bed. 14. Process according to claims 8 and 13, characterized in that the granules obtained after drying are sprayed with small quantities of liquid compounds commonly used in detergent compositions. 15. Process according to claims 8 and 14, characterized in that the forming agent in the form of aqueous solution of concentration 10 ... 60% by weight of alkali metal silicate, measured in the dry state, is sprayed onto the detergent powder from the base of the tower. or on the mixture of ingredients of the detergent composition, the ratio of dry weight silica / detergent powder or ingredient being between 1/100 and 30/100, and the dry weight / water weight ratio associated with silicate granules is 100/120. ..100 / 140.