BG61772B1 - Structureforming agent for detergent compositions, method for its prparation and use, spherical cogranules and method for their preparation - 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

Technical field

The invention relates to a structure-forming agent for alkali metal silicate based detergent compositions, to a method for its preparation and use, to spherical granules and a method for their preparation. The structure-forming agent is used for detergent compositions, in particular washing powders, for washing laundry or for washing machines.

BACKGROUND OF THE INVENTION

Structuring agent means any active additive that improves the effectiveness of the surfactants of the detergent composition.

The structure-forming agent must soften the water used for washing, to remove the calcium and magnesium present in the water in the form of soluble salts and in the soiled linen in the form of complexes which are more or less soluble. The removal of calcium and magnesium can be accomplished by complexation, by the formation of solutes, by ion exchange, by precipitation. Sedimentation should be controlled to avoid inlay on the laundry or washing machine components.

This control of precipitation is achieved by water-soluble polymers having an affinity for calcium and magnesium.

The structure-forming agent should contribute to the effect of the surfactants with respect to oily contaminants, to have a dispersing effect against pigmented contaminants such as metal oxides, silica, dust, humus, limestone, soot, etc.

This dispersion effect is usually achieved by the presence of polyanions, which give a high density of negative charges to the interfacial surfaces.

The structure-forming agent must confer a favorable ionic strength on the functioning of the surfactants, in particular by increasing the size of the micelles. It should carry OH ions for saponification of fats and for the increase of negative surface charges on textile surfaces and on specific impurities.

Silicates have long been considered good detergent additives, especially in connection with tripolyphosphates, as described in US-A-2 909 490, but they are little used without phosphates for washing laundry.

Detergent compositions containing silicates in a ratio of SiO ₂ : Na ₂ O between 0.9 and 1.6, preferably in the order of 1, sodium carbonate, tripolyphosphate and copolymers of acrylic and maleic acid are known from EP-A-353 562 .

The most commonly used silicates have a molar ratio of SiO ₂ : Na ₂ O between 1.6 and 2.4. They are commercially available in the form of concentrated solutions of 35-45% by weight of dry matter or in the form of finely divided powdered silicate, optionally extruded.

Commercial concentrated solutions are most commonly obtained from amorphous silicate, called vitreous or soluble glass.

These soluble glasses were dissolved in water in a pressure autoclave at 140 ° C. Thus, commercially available dry substance solutions are about 45 wt% for silicate at a ratio of 2 and about 35 wt% for silicate at a ratio of 3.5.

The concentrated silica solutions are introduced by the manufacturer of the detergent into an aqueous suspension containing the other ingredients of the detergent. The suspension is then triturated. The silicate, ground and dried with the other ingredients, contains no more than 20% bound water relative to its dry weight, even less.

The silicates used in the commercially available powder form are obtained by pulverized drying of concentrated solutions of glassy silicate, and it is necessary to retain 20 to 22% by weight of water with respect to the final product in order to ensure its good solubility.

It has been found that when silicate is used as a solution in the washing bath in an amount of 1 to 3 g / L, this powdered silicate which does not contain more than 20-22% bound water (relative to the final product) has poor structure-forming properties.

Powdered silicate in solution gives many silicon monomers of formula

Si (OX) ₄ in which X is H or Na, which have no structure-forming effect. These monomers do not re-associate to form polyanions unless the concentration of silica is at least 50 to 500 g / L and then slowly.

Such concentrations of silicate as well as the slow kinetics of polymerization of the monomers are not compatible with the conditions and duration of washing in a washing machine.

The set for powders containing 20-22% bound water (relative to the final product) is also valid for compositions containing silicate with 20% bound water (relative to dry silicate), which are obtained by introducing a concentrated solution of silica into the suspension of the other constituents and then drying.

DE-A-2 322 123 describes a process for the preparation of silicate carbonate particles, which consists of contacting a silicate solution with carbonate particles and drying the mixture to remove silica water vapor.

FR-A-2 143 093 describes a method for simultaneous spray drying of silicate mixed with the addition of sodium carbonate. The process is carried out at a temperature of 300450 ° C so that the water contained in the silica is evaporated and removed.

US-A-4 761 248 describes a process for the preparation of hydrated particles from anhydrous hydrating composition and a solution of silicate, the water of the latter providing for the hydration of the hydrating composition.

US-A-4 427 417 describes a mixture of agglomerated hydrating particles of detergent and a solution of silicate, the latter being used to hydrate the hydrating compositions, which are then dried.

SUMMARY OF THE INVENTION

According to the invention it has been found that when a detergent composition is used in a detergent composition made up of alkali metals, in particular sodium or potassium silicates, rich in species in which the silicon atoms are in the form of Q ₂ and Q ₃ , the polyanions formed at dilution 1 up to 3 g / L in a laundry medium have a durability sufficient to act as a structure-forming agent in the detergent. In the form of Q ₂ of silicon, it is understood that each silicon atom is involved in two bonds -Si-O-Si- and the other two have terminal groups -Si-O-O, where X is an alkali metal or H, and a form Q ₃ of silicon means that each silicon atom has three bonds -Si-O-Si- and the remaining bond has a terminal group -Si-OX.

The structure forming agent of the present invention is composed of an alkali metal silicate, in particular potassium or sodium, containing at least 30%, preferably at least 50%, and silicon atoms in the form of Q ₂ and Q ₃ .

Said silicate may have a molar ratio of SiO ₂ : M ₂ O in the range of 1.6 to 3.5, preferably 1.8 to 2.6.

The structure may be in different structured (dust, granules ...) or unstructured form.

An embodiment of the invention is a structure forming a 10-60% aqueous solution, preferably 3550% by weight of a dry residue of an alkali metal silicate, in particular sodium or potassium, with a molar ratio of SiO ₂ : M ₂ O in the range between 1.6 and 3.5, preferably 1.8 to 2.6.

The concentrated solution of an alkali metal silicate used as a structure-forming agent is preferably obtained by dissolving soluble glasses in an autoclave in water at a pressure and temperature of 140 ° C and then possibly diluting it; it can also be obtained by other known methods, for example by direct treatment of sand with a concentrated solution of caustic soda (sodium hydroxide solution).

NMR shows that:

- solution with 45% dry glassy silicate content and a SiO ₂ molar ratio: Na ₂ O = 2 contains 34% of Q ₃ species, 51% of Q ₂ species, 12% of Q species, and 3% of Q _o species;

- a solution with 35% dry residue and a ratio of 3.5 contains 46% of species Q ₃ , 27% of species Q ₂ , 16% of species Q ₄ , 9% of species Q ₁ and 2% of species Q _o .

The structure-forming solution can be used by further spraying on the laundry detergent outlet, in the case of atomisation installations or on the mixture of the laundry detergent ingredients in the case of the dry mixture, and so that it is absorbed by the powders. The resulting spray mixture, if necessary, is moderately dried in such a way that the weight ratio of dry silicate water remaining attached thereto is between 100: 120 and 100: 40, preferably between 100: 90 and 100: 50.

The amount of silica solution used is such that the weight ratio between dry silicate and detergent powder is between 1: 100 and 30: 100. preferably between 10: 100 and 20: 100.

Another embodiment of the invention which does not limit it consists in a 10 to 60% aqueous solution, preferably a 35-50% (w / w) dry residue of an alkali metal silicate, in particular sodium or potassium , with a molar ratio of SiO ₂ : M ₂ O in the range of 1.6 to 3.5, preferably 1.8 to 2.6, adsorbed and / or absorbed on a finely divided carrier, inert with respect to silica, such as a weight ratio of silica, expressed as dry matter water remaining bound to the silica is from 100: 120 to 100: 40, preferably from 100: 90 to 100: 50. "Inert" means chemically inert.

The term "bound" to silica water refers to water from a carrier solution that is not bound to the mineral carrier, namely in the form of crystalline hydrate.

Inorganic carriers of the silicate solution are water-soluble compounds such as: sodium carbonate, sodium sulfate, sodium borate, sodium perborate, sodium metasilicate, phosphates or polyphosphates, such as sodium phosphate, sodium tripolyphosphate, and these carriers may or may be used alone.

The carrier typically represents 55 to 95%, preferably 65 to 85%, of the weight of the solution expressed as dry matter (i.e., the weight of the solution expressed as dry matter + the weight of the carrier).

The applied solution can be obtained by adsorption and / or absorption by contacting a concentrated aqueous solution of an alkali metal silicate with a molar ratio of SiO ₂ : M ₂ 0 between 1.6 and 3.5, preferably between 1.8 and 2.6 and having a dry residue of between 10 and 60%, preferably between 35 and 50%, with an inorganic carrier inert to silica, the carrier being such that the water remaining bound to the silica after adsorption and / or absorption corresponds to the weight ratio between silica, expressed as dry matter and water Associated with the silicate ranging from 100: 120 to 100: 40, preferably between about 100: 90 to 100: 50.

Contact can be accomplished by adding, in particular by spraying, the concentrated silica solution onto the carrier in the form of small particles in any finely ground mixer, namely the LODIGE type or in pelletizing devices, discs ...), at a temperature between 20 and 95 ° C, preferably between 70 and 95 ° C.

The carriers that can be used are listed above.

The amount and concentration of the silica solution to be used depend on the absorbent and / or adsorptive capacity of the carrier, taking into account the potential for the carrier to form crystalline hydrates; the amount of silica-free water can be in the form of a hydrate in the carrier and can be determined by differential thermal analysis or by quantitative X-ray diffraction. The water, possibly attached to the carrier in a form other than defined hydrates, can be determined by suitable physicochemical means (thermoporosimetry, thermogravimetry, proton NMR, infrared spectroscopy).

The adsorption and / or absorption capacity of the carrier can be determined according to known methods, for example by measuring the variation of the slip angle at the base, as a function of the amount of silica solution added.

If necessary, the mixture consisting of the carrier and the silica solution can be dried but moderately and in such a way that the desired amounts of silica bound water are achieved.

The resulting particles of the carrier on which the silica solution is applied can be ground, if necessary, in such a way that an average diameter of between 200 and 800 µm is obtained.

Alkali metal solutions adsorbed and / or absorbed on alkali metal carbonate and representing spherical granules of hydrated alkali metal silicate and alkali metal carbonate represent the structure forming agent of the invention.

Spherical co-granulates of hydrated alkali metal silicates and alkali metal carbonates may be prepared according to a method in which an aqueous solution based on alkali metal silicates or based on a mixture of silicates and alkali metal carbonates is atomized onto a moving layer of particles based on alkali metal carbonates passing through a rotary granulation device, such as particle velocity, moving layer thickness, and flow rate of spray solution such that each particle with is converted into a plastic granulate, coming into contact with other particles. The resulting co-granulates are subjected to compaction, after which the compressed granules are dried to obtain a content of silica bound water corresponding to a weight ratio of dry silicate to bound water between 100: 120 and 100: 40.

Alkali metal silicates and carbonates can be cited, preferably sodium and potassium, and especially sodium.

A nebulized aqueous solution based on silicate or on the basis of a mixture of silicate and carbonate may have a dry residue content of between 30 and 55% by weight, preferably between 30 and 45% by weight; the alkali metal silicate has a molar ratio of SiO ₂ : M ₂ O between 1.6 and 3.5, preferably between 1.8 and 2.6 and most often close to 2; the carbonate is contained in an amount depending on the desired end product.

The solution of the solution based on silicate or on the basis of a mixture of silicate and carbonate is carried out at a temperature between 20 and 95 ° C, preferably between 70 and 95 ° C; this can be facilitated by the simultaneous introduction (for example by means of a diffusion nozzle) of pressurized air and at a temperature of the same order.

The particles used to produce co-granulates. consisting mainly of alkali metal carbonate, having an average diameter of 10 to 150 μ, preferably 20 to 100 μ, and in particular 30 to 80 μ, a bulk density of non to bulk density of 0.4 to 1.1 g / cm ³ , preferably 0.6 to 1.1 g / cm ³ , a water content of 0.05 to 0.4%, preferably 0.1 to 0.3 wt%, insoluble matter content from 5 to 100 mg / kg, usually from 10 to 60 mg / kg.

Ordinary or milled carbonate of ordinary quality may be used.

Along with the carbon particles, small amounts (less than 10 wt.% By weight of the co-granules) may be present, such as anti-precipitation polymers (carboxymethylcellulose), enzymes commonly used in the field of purification technology having a diameter and density close to each other. to those of the carbon particles.

The atomizing co-granulation device can be any kind of rotary device of the types: rotary discs, dragee receiving device, rotary drum, mixer granulator.

One preferred method of producing co-granulates is to use a rotary granulator to allow the particles to pass into a thin layer. Devices for producing dragees with an axis of rotation inclined with respect to the horizontal at an angle greater than 20 °, preferably greater than 40 °, are particularly suitable; their geometry can be quite different: cross cone, flat, stepped, a combination of the three forms.

Another preferred method of producing co-granulates is to use a rotary drum having an inclination angle of at least 3% and preferably 5%.

The carbon-based particles pass at a temperature in the range of 15 to 200 ° C, preferably 15 to 120 ° C and most often between 15 and 30 ° C.

The amounts of the solution based on silicate or on the basis of the silicate / carbonate atomizer and the carbonate-based particles correspond to the ratio between the liquid flow rate and the particle flow rate of

0.2 to 0.8 l / kg, preferably 0.4 to 0.7 l / kg and most often from 0.62 to 0.7 ί / kg, these values being expressed in sodium salts.

The flow rate of the nebulized solution, the rate of passage of the particles, and the thickness of the particle layer are such that each particle absorbs the liquid and agglomerates with the other particles with which it comes into contact to form a plastic granulate rather than a slurry.

The rate of passage of the particles and the thickness of the layer are controlled by the flow 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 disk or drum unit is typically between 15 and 40 minutes.

It is up to each person skilled in the art, depending on the starting materials, to adapt the apparatus used to obtain the desired product; namely, for a dragee device, the geometry (truncated cone, flat or stepped or a combination of the three shapes), dimensions (height, diameter), slope angle, rotation speed and relative position of the solid and liquid feeders are adjusted .

The drum shall observe the geometry (diameter of the cylinder), the angle of inclination, the speed of rotation, the loading of the cylinder and the relative location of the solid and liquid feeders.

The resulting non-compacted and non-dried granules have characteristics that are a function of the conditions used to conduct the granulation. Usually they are: a silicate content of 7 to 30 wt.%, Preferably 11 to 23 wt.% And most often 21 to 23 wt.%, A carbonate content of 41 to 75 wt.%, Preferably of 48 to 64% by weight and most often from 48 to 51% by weight and a water content of 18 to 29%, preferably from 25 to 20% by weight and most commonly from 27 to 29% by weight.

The compaction can be carried out at room temperature by passing the granules obtained during the granulation step through a rotary device, which should preferably be separate from the granulation.

The compacting step can conveniently be carried out by inserting and stopping the granules into a rotating drum. The inclination angle of the latter is at least 3%, preferably at least 5%. The size of this drum, its rotational speed and the residence time of the co-granulates depend on the desired density: the residence time is usually between 20 min and 3 h, preferably between 20 and 90 min.

Mixer granulators are also suitable for the compaction process.

The co-granulation and compaction processes may also be carried out in the same device, for example, in a step-like device for receiving dragees, the compaction of the co-granulates being achieved by passing them through the last steps of the apparatus; in addition, these two operations can be performed in a two-section drum.

The compacted granules thus obtained are dried in known ways. A particularly successful method is the fluidized-bed drying using air and at a temperature between 40 and 90 ° C, preferably between * 60 and 80 ° C. This process is carried out for a time which is a function of the air temperature, the water content of the granules exiting the granulation apparatus and the desired water content of the dried granules, as well as the fluidization conditions; these conditions can be adapted depending on the desired product.

The dried compacted granules have a silicate content of 8 to 38 wt.%, Preferably 14 to 31 wt.% And most often 24 to 31 wt.%, A carbonate content of 47 to 87 wt. %, preferably from 59 to 81 wt. % and most often from 64 to 69% by weight, water content from 5 to 25% by weight, preferably from 7 to 20% by weight and most often from 12 to 20% by weight, bulk density without compaction of 0.7 to 1.5 g / cm ³ , preferably from 0.75 to 1.5 g / cm ³ and most often from 0.8 to 1 g / cm ³ and average diameter (in terms of percentage of particles passed) from 0.4 to 1.8 mm, preferably from 0.6 to 0.8 mm with a deviation of log ₁₀ type from 0.02 to 0.3, preferably from 0.05 to 0.1.

These co-granulation / compaction / drying steps allow the preparation of co-granulates based on hydrated silicates and alkali metal carbonates, which are completely spherical, dense and rapidly soluble in water.

Spherical co-granulates based on hydrated sodium silicates and sodium carbonate, which are particularly suitable for the preparation of detergent compositions for dishwashers contain, in% by weight: silicate 24 to 31, carbonate 64 to 69, water 12 to 20. They have a bulk density without compaction of 0.7 to 1.5 g / cm ³ , preferably 0.8 to 1 g / cm ³ , with an average diameter of 0.4 to 0.8 mm, with a deviation of log ₁₀ type from 0.05 to 0.1, and a dissolution rate of up to 90% in water of less than 2 min and up to 95% of less than 4 min.

A dissolution rate of up to 90% or 95% in water refers to the time required to dissolve 90 or 95% of the product at a concentration of 35 g / l in water at 20 ° C.

When structured (powder, granulate ...), the structure-forming element of the invention is used in dishwasher detergent compositions in an amount of from 3 to 90% by weight, preferably from 3 to 70% by weight of said compositions; the amounts used for formulations intended for dishwashing are from 3 to 60% by weight, preferably from 3 to 40% by weight, of the compositions in question (these amounts are expressed as the weight of dry silicate by weight of the composition ).

Along with the structure-forming agent of the present invention, at least one surfactant in an amount of 8 to 20%, preferably 10 to 15% by weight, of the composition is present in the laundry composition.

Examples of surfactants are anionic surfactants such as alkali metal soaps (alkali salts of C ₈ -C ₂₄ fatty acids), alkaline sulfonates (alkylbenzenesulfonates with C ₈ -C ₁₃ , alkyl sulfonates with C ₁₂ C _{] 6} ). oxyethylated and sulfated C ₆ -C ₁₆ fatty alcohols, oxyethylated and sulfated C ₈ -C ₁₃ alkyl phenols, alkaline sulfosuccinates (C ₁₂ C ₁₆ alkyl sulfosuccinates); non-ionic surfactants of the C ₆ -C ₁₂ polyoxyethylated alkylphenols type, C ₆ -C ₂₂ oxyethylated aliphatic alcohols, propylene oxide block copolymers of carboxyamides, optionally polyoxyethylated; amphoteric surfactants of the alkyldimethylbetaine type; cationic surfactants such as alkyltrimethylammonium chlorides or bromides, alkyldimethylethylammonium.

Other ingredients may be present in the laundry composition such as:

- structure forming devices of the type:

- phosphates, in an amount up to 25% of the total weight of the composition,

- zeolites up to about 40% by weight of the total composition,

- sodium carbonate up to about 80% by weight of the total composition,

- nitrilacetic acid up to 10% by weight of the total composition,

- citric acid, tartaric acid up to 20% of the total weight of the composition, the total amount of structure forming agent being from 0.2 to 80%, preferably from 20 to 45% of the total weight of the detergent composition,

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

- carboxymethylcellulose-type anti-precipitation agents, methylcellulose in an amount up to 5% of the total weight of the detergent composition,

- anti-scale agents of the type of copolymers of acrylic acid and maleic anhydride in an amount up to 10% of the total weight of the detergent composition,

- Sodium sulphate fillers for powdered detergents in an amount up to 50% of the total weight of the detergent composition.

The following examples illustrate the invention without limitation.

Examples 1 to 5.

Results for the structure builder.

- solution of sodium silicate with a molar ratio of SiO ₂ : Na ₂ O = 2 with 45% by weight of dry residue (example 2)

- a solution of sodium silicate with a molar ratio of SiO ₂ : Na ₂ O = 3.4 with 35% by weight of dry residue (example 4) was measured in TERGOTOMETRE (US Testing Company, Hoboken, USA), in a binary mixture with anionic surfactants substance LABS (linear sodium dodecylbenzenesulfonate, manufactured by ALDRICH), the reflection being measured with a GARDNER reflectometer.

These results are compared with:

- LABS 2 g / l only (Example 1)

- atomized silicate powder with a ratio of 2 containing 22% water (ie 28.2% water relative to dry silicate) (example 3)

- atomized silicate powder with a ratio of 3.4 containing 18.6% water (ie 22.8% water relative to dry silicate) (Example 5) used under the same conditions (4 g / l).

The results of these measurements are presented in Table 1.

Measurement method

Principle: Washing in a simplified machine in a tergotometer, washing at 65 ° C with normally contaminated surfactant tissues and the structure builder under test. The laundry lasts 20 minutes and the color of the fabric is measured before and after washing. A white sample is made, washing the same type of fabric with only a surfactant to calculate the efficiency of the test builder.

How it works: The thermometer is a 4-pot stainless steel apparatus with pulsators that are controlled at 100 cycles per minute. The vessels were placed in a bath with water regulated at 65 ° C.

1) 1 1 solid tap water (34 ° TN French) was placed in each vessel. When the water reaches the desired temperature, enter:

- five samples of 10 x 12 cm white cotton, 405 W style, manufactured by Test Fabric,

- two samples 10 x 12 cm of cotton contaminated with EMRA (mixture of Chinese ink and olive oil) of product GALLEN 101,

- two samples 10 x 12 cm of cotton contaminated with red wine, product 114 of GALLEN,

- two samples of 10 x 12 cm polyester cotton (PES) contaminated with EMPA, article 104 of GALLEN,

2) The following three operations are carried out simultaneously:

- turn on the stopwatch

- enable stirring

- Addition of Structural / Surfactant mixture

- the structure forming agent is tested at 4 g / Ι (mass is reported as dry matter from the product) and 2 g / 1 LABS is added

3) Crying

After 20 min, the laundry water is discarded and the tissues are rinsed with 3 x

1 cold tap water.

4) Drain and dry

Samples are drained, dried, individually placed in absorbent paper. The fabrics are then passed twice between a gloss press between two sheets of absorbent paper at a temperature of about 110 ° C.

5) Color measurement.

The GARDNER apparatus is calibrated by measuring the zero with a black plate designed for this purpose and then reading the values L, a, b on a white normalized plate of the same type as the black one.

L has color ranging from black to white.

L = 100 corresponds to a white sample

L = 0 corresponds to a black sample a has coloration between colors green to red a> 0: coloration is red a <0: coloration is green b has coloration between colors yellow to blue b> 0: coloration is yellow b <0: the color is blue

After calibration, appropriate measurements are made. Two samples of each type of fabric are taken from each vessel and 5 measurements are made for each sample (ie one in the center and one in the four corners), placing a heavy metal plate on the fabric, followed by the middle arithmetic of the ten measurements. In the same way, it is treated with non-washed fabrics.

6) Using the results

DL and DE are calculated for each trial and for each tissue type.

DL = L after washing - L before washing

Da = a before laundry - and after laundry Db = b before laundry - b after laundry DE = DLMDa ^ t-Db ² "Cleaning The mean of DL and DE for each product and each type of contaminated fabric is calculated.

It is then calculated for each product: EMRA cotton cleaning = DE average for EMRA cotton cleaning of EMRA RES = DE average for EMRA cotton cleaning of wine = DE average for cotton of wine cumulative cleaning = sum of EMPA cotton cleanings, EMRA PE, wine cotton.

Examples 6 and 7

The LODIGE M5G mixer (commercial product of LODIGE) is charged with 800 g of anhydrous tripolyphosphate (TPP) H ₂ , commercial product of RHONE - POULENC.

After the apparatus was started to rotate at a speed of 400 rpm, 200 g of sodium silicate solution with a molar ratio of SiO ₂ : Na ₂ O = 2 and a dry residue content of 45% were introduced by atomization.

This addition continued for 10 min; after another 10 minutes of stirring, the product was drained and allowed to stand in an open air vessel at room temperature.

The product has TPP partially hydrated 82 wt%, sodium silicate 92 wt% and silica bound water 9 wt. % or 100% with respect to the dry silicate.

Determine the total amount of water contained in the product by measuring the weight loss of the latter when heated to 500 ⁱⁿ C; the amount of hydrate bound in the form of hydrates is also measured by differential thermal analysis.

The amount of bound water is calculated as the difference between the total amount of water and the water bound in the form of a hydrate. The average diameter is 250 pm.

The results for this structure-forming product were determined according to the methods described above, replacing the two samples of EMP contaminated article EMPA 104 with two cotton samples contaminated with WFK by KREFELD of the same size (Example 6).

These results are compared with those obtained for a powder mixture of anhydrous TPP H and atomized silicate with a ratio of SiO: Na ₂ 0 2 and 22% water at a weight ratio between TPP and dry silicate 800: 90 and under the same conditions (4 g / Ι) (Example 7).

The results of the measurements are presented in a table

Table 1

Example 1 LABS 2 g / l 2 LABS 2 g / l R2 sol. 4 g / l 3 LABS 2 g / l R2 sol. 4 g / l 4 LABS 2 g / l R2 sol. 4 g / l 5 LABS 2 g / l R2 sol. 4 g / l EMRA cotton cleaning 17,20 19.53 20,23 21.03 21.09 EMRA RES 10.53 21.61 20,93 21,29 18,89 cotton from wine 17,28 20,48 18,44 20.09 20,28 cumulatively 45.07 61.62 59,00 62.41 60.86

Table 2

Example 6 LABS 2 g / l R2 solution applied to TPP 4 g / l 7 LABS 2 g / l R2 atomized + TPF 4 g / l Cleaning white cotton -0,20 0.06 cotton from KREFELD 14.15 13,47 EMRA cotton 25.14 25.42 cotton from wine 19,67 18,77 cumulatively 58.96 57.66

Example 8. The granulation system is a flat-plate disk of 800 mm diameter and 200 mm depth. During granulation, the rotational speed is about 35 rpm and the angle of inclination of the axis of rotation with respect to the horizontal is about 55 °. The granulating disk is continuously fed at a flow rate of 21.4 kg / h with fine particles of sodium carbonate, the main characteristics of which are as follows: titratable alkalinity: 99.01%, water content 0.12% by weight, bulk density without compaction 0 , 50 g / cm ³ , mean diameter 95 μ and insoluble substances 58 mg / kg.

This powder, which is rotated in the granulation disc, is sprayed with sodium silicate at a flow rate of 13.4 l / h and air at 80 ° C with a bifluid nozzle located at a distance of 20 cm from the bottom of the granulation disc. the device for receiving the dragees. The amount of active ingredient and the SiO ^ NaJ) ratio of the nebulized solution were 43 and 2% by weight, respectively.

The average residence time of the particles in the disc is 10 to 15 min. The disc exit particles have a room temperature.

The granules protruding from the disk are fed into a rotating cylinder with smooth walls and a diameter of 500 mm and a length of 1300 mm, which is inclined at an angle of about 5 °. The outlet diaphragm is adjusted so that the average residence time of the particles is about 40 minutes. The speed of rotation of the drum (18 rpm) is so selected that a layer of moving particles is obtained, which facilitates the compaction of the latter.

The granules thus obtained are dried in a fluid bed and at a temperature of about 80 ° C (fluidization air temperature is 85-90 ° C) for 10 to 15 minutes.

The dried product thus comprises, in wt%: carbonate 85, silicate 21 ± 0.5 and water 13.5.

Its bulk density without compaction is 0.90 g / cm ³ . It has a weight of 1 mm 10.8% by weight, an average diameter of 0.73 mm, passing through 0.2 mm - 6%.

90% by weight of the product were dissolved in 50 s (aqueous solution 35 g / l at 20 ° C), 95% w / w. of the product were dissolved in 65 s (aqueous solution 35 g / l at 20 ° C). The product has a whiteness of L90,3 and a tensile strength of 7%.

Granules are very suitable for storage.

Measurement of tensile strength

A flurometer, a standardized apparatus used for grading hydraulic connections, is described and described in French standard P 15-443.

Way of working:

g of the product is screened with 1200 and 180 μ sieves using a ROTO-LAB sieve laboratory machine (FROLABO commercial product).

Particles between 180 and 1200 μm are separated.

Weigh exactly 25 g of the test product; M is the exact mass.

They are placed in the fluorometer.

Weigh a SOXLHET filter (FROLABO commercial product) empty and dry and place it on top of the fluidization tube; Ml denotes its mass.

Fluidized for 5 min (dry air flow rate 15 l / min).

Collect the product that has flown into the filter, as well as the fine particles, possibly deposited on the vertical walls of the fluidization tube using a diameter-appropriate seal. Weigh in and M2 denotes the mass of the fine particles and the filter.

The remainder of the bottom of the fluidization tube is again sieved with ROTO-LAB and particles smaller than 180 μ are separated and weighed; M3 denotes the mass of these fine particles.

Calculation. Presentation of the result:

The degree of comminution is equal to the percentage of fine particles <180 μ obtained during the product fluidization process.

Erasing% - (MH + M2-M1) x 100

M

Example 9. The steps described in example 1 were repeated with the following modifications:

Granulation:

- granulation disk: rotation speed 30 rpm

- Powder supply: 22 kg / h

- feed with silicate solution: 13 l / h.

Compaction:

- Drum speed: 10 rpm.

Fluidized bed drying:

- temperature - 90 ° C

- duration: 20 min.

The dried product thus contains, by weight,% carbonate 80.9, silicate 22.9 ± 0.5 and water 16.1.

Its bulk density without compaction is 0.86 g / cm ³ . It has a sieve through 1 mm - 2.8% by weight, an average diameter of 0.64 mm, passing through 0.2 mm - 7.3%.

90% by weight of the product were dissolved in 75 s (aqueous solution 35 g / Ι at 20 ° C), 95% wt. dissolved in 102 s (aqueous solution 35 g / Ι at 20 ° C). The product has an L-95,6 whiteness and a tensile strength of 9.2%.

Granules are very suitable for storage.

EXAMPLE 10 A granulation system is a drum rotating at 40 rpm with smooth walls 500 mm in diameter and 1300 mm in length, which slopes about 7.5%. The outlet diaphragm is adjusted so that the residence time of the particles is between 15 and 20 min.

The drum was fed continuously at a flow rate of 37 kg / h of powdered carbonate having the same characteristics as in Examples 1 and 2.

A silicate solution (with an active substance content of 45.6% by weight) was sprayed onto this powder material rotating in the drum using 80 ° C air through a flat-tip bifluid nozzle located in the lower third in the drum. and a weight ratio of SiO ₂ : Na ₂ O-2 with a temperature of 80 ° C and a flow rate of 18 1 / h.

The co-granulate at the exit of the drum is at room temperature and has a density of 0.68 g / cm ³ .

The co-granulate is compacted gradually over 1 hour in a smooth-walled rotating drum 500 mm in diameter and 1300 mm in length and 5% inclined.

The drum speed is 20 rpm.

The granules thus obtained are dried in a fluid bed at a temperature of about 65 ° C (fluidizing air temperature is 70 ° C) for 15 min.

The dried product thus contains, by weight,% carbonate 62, silicate 20.5 ± 0.5 and water 17.6.

Its bulk density without compaction is 0.82 g / cm ³ , the 1 mm unweighted density is 5% by weight. It has an average diameter of 0.65 mm, passing through 0.2 mm - 0.6%.

90% by weight of the product were dissolved in 50 s (aqueous solution 35 g / Ι at 20 ° C), 95% wt. of the product were dissolved in 63 s (aqueous solution 35 g / Ι at 20 ° C).

Granules are very suitable for storage.

Example 11. The operations described in example 3 are repeated with the following modifications:

Compaction

- continuously for 2 hours.

The dried product thus contains, by weight,% carbonate 60.8, silicate 19.3 ± 0.5 and water 19.9.

Its bulk density, without compaction, is 0.91 g / cm ³ , and the non-compacted density is 1.6% by weight. It has an average diameter of 0.57 mm and passing through 0.2 mm - 1.22%.

90% by weight of the product dissolved in 37 s (aqueous solution 35 g / Ι at 20 ° C), 95% wt. dissolved in 45 s (aqueous solution 35 g / Ι at 20 ° C).

Granules are very suitable for storage.

Examples 12 and 13. The properties of the co-granulator of Example 8 were measured according to the method described in Examples 1 to 5.

They are compared to those of a mixture of powdered sodium carbonate and atomized powdered sodium silicate in a ratio of SiO ₂ : Na ₂ 0-2 containing 22% water in the final product, i. 20.2% water relative to dry silicate, at a weight ratio of 3: 1 (carbonate: atomized Rp.

The results are presented in Table 3.

Table 3

Example 12 LABS 2 g / l co-granulate 4 g / l 13 LABS 2 g / l carbonate 3 g / l R 2 atomized 1 g / l Cleaning up EMRA cotton 19,27 17,83 EMRA RES 24.52 23.13 cotton from wine 19,20 19,49 cumulatively 62.99 60.24

The amounts of carbon and silica, 15 presented in the table, are expressed as dry residue.

The properties of the co-granulates are found to be better than those of the powder mixture with the same ratio of silicate to carbonate.

Example 14. In the LODIGE M5G mixer as described in Examples 6 and 7, starting particles were obtained from: 1800 g light sodium carbonate with an average diameter of about 110 μπι, 1200 g 25 sodium silicate solution with a molar ratio of SiO ₂ : Na. O 3.4 and 37% dry residue.

After 5 minutes of addition of the silica solution, 5 additional minutes of mixing and standing of air for 2 h 30 at room temperature, a product was obtained comprising by weight%: sodium carbonate 60, silicate 20 and silica bound 20 ( or 100% for dry silicate).

The average diameter is 400 μπι.35

This product is mixed dry with the following additives to obtain a dishwashing composition:

Composition of detergent wt.h. linear alkylbenzenesulfonate 25 40 CEMULSOL DB 618 3 CEMULSOL LA 90 (surfactant on S.F.O.S) 2 zeolite 4A 18 45 the product of Example 14 25,8 SOKALAN CP5 (B.A.S.F copolymer) 4 carboxymethylcellulose 1.5 T1NOPAL DMSX 0.2 50 T1MOPAL SOF (CIBA-GEIGY bleach) 0.2

RHODORSIL 204442 (RHONEPOULENC antifoam) sodium perborate, 4H ₂ 015

TAED3 pH (10 g / Ι) - 10.25

The pollution abatement test is conducted in a FOM 71 washing machine manufactured by WASCATOR.

The test conditions are as follows:

- cycle used: 60 ° C

- total cycle time: 70 min without prewash

- number of cycles: 3 for detergent

- water hardness: 32 French hydrotimetric degrees

- amount of laundry: 3,5 kg white cotton towels

- tested fabrics: two batches of the following fabrics are affixed to each laundry, affixed with pins to the towels:

Gray Cotton: Test-Fabric

Krefeld 10C

IEC 106 EMPA 101

Gray Polyester / Cotton: Test-Fabric

Krefeld 20C EMPA 104

Protein Spots: Blood (EMPA 111) Cocoa (EMPA 112) Mixture (EMPA 116)

Oxidizing Stains: Tea (Krefeld 10G)

Ecru Cotton (EMRA 222) Wine (EMRA 114)

Detergent dosage:

1st batch: 5 g / Ι or 5 x 20 - 100 g per wash

2nd batch: 8 g / Ι or 8 x 20-100 g laundry 5

Method for determining the removal of dirt and stains

Photometric measurements (measurement of the amount of light reflected from a tissue) allow to calculate the percentage of 10 pollution removal. An ELREPHO 2000 machine manufactured by DATACALOR is used.

The removal of contamination is expressed by the formula: 15% removal - C-B x 100 αΊΓ in which A is a reflection of a white witness sample, B is a reflection of a sample of a contaminated witness, C is a reflection of a contaminated sample 20 after washing.

Reflections are determined using trichromatic blue without optical whitening effect.

Number of measurements taken per sample 25 ba - 4.

Number of laundry samples - 2.

Number of laundry - 3 or 4 x 2 x 3 - 24 measurements of contamination, product and concentration tested.

Anti-boiling tests are carried out on a SCHULTESS SUPER drum machine

DE LUXE.

The test conditions are as follows;

- cycle used: 60 ° C

- total cycle time: 65 min, without prewash

- number of cycles: 25 washes

- water hardness: 21.2 French hydrotimetric degrees

- woven fabrics used: a witness band that exactly meets the specification of NFT 73. 600

- amount of laundry: 3 kg of 100% cotton wipes

- amount of detergent: 5 g /

1.

Samples that have undergone 25 laundry are dried, weighed and calcined to 900 ° C.

The percentage of the weight of the ash relative to the weight of the initial samples is determined.

The individual test results are presented in Table 4.

Example 15. A detergent analogous to that of Example 14 was obtained as the structure-forming mixture of zeolite 4A, the product of example 14 SOKALAN CP5 being replaced by the following structure-forming mixture in parts by weight: zeolite 4A 30, atomized silicate R. 3, light carbonate 6, sodium sulfate 4,8 and SOKALAN CP5 4.

The results of the dirt removal and anti-scale properties tests are presented in Table 4.

Table 4

Example 14 15 Cleaning cotton 5 g / l 57.7 50.5 cotton 8 g / l 62.5 58,2 PEC 5 g / l 38,4 36,6 PEC 8 g / l 46,7 44.5 protein 5 g / l 42.6 46.6 protein 8 g / l 50.8 54,1 whitening 5 g / l 43,9 37,3 whitening 8 g / l 57,9 45,3 deposition 5 g / l 0.69 0.85 average value 5 g / l 45.65 42.75 average value 8 g / l 54.47 50.02

Examples 16 to 18. The product of Example 8 was mixed with additives in LODIGE M5G to obtain a dishwasher composition.

These formulations are presented in Table 5 5 and tested in a MIELE dishwasher whose water softener has not been regenerated, and therefore it supplies calcined water with a total hardness of 30 ° TH French.

With each of the formulations used in an amount of 3 g / Ι water, 10 plate washes were washed on sodium-calcium beakers.

The plates are then photometrically measured using an apparatus

GARDNER identical to that used in Examples 1 to 5.

Measure the total amount of light L reflected from the sample.

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

When L is between 7 and 14, a slightly visible veil is observed.

The product of Example 8 was compared with a close composition in a mixture of sodium carbonate and BRITSIL H2O co-granulates (SiO ₂ : Na ₂ 0-2 and containing 20% water - a commercial product of PHILADELPHIA QUARTZ).

The results are presented in Table 5.

Table 5

Example 15 16 17 The co-ordinate of Example 8 59 54 - Co-granulated sodium carbonate - - 31 BRITSIL H2O - - 17 Sodium citrate 17 20 25 Mw-4500 sodium polyacrylate 4 5 5 Sodium sulfate 4 5 8 Non-ionic surface- active agent 2 2 2 Sodium parborate, 1 H 2 O 10 10 10 TAED 2 2 2 Enzymes 2 2 2 L 5,3 5.2 5.2

The use of the co-granulates of Example 8 is found to reduce the amount of sodium citrate that is expensive and of polyacrylate that is non-biodegradable.

Claims (27)

Claims A detergent composition forming agent, characterized in that it is an alkali metal, in particular sodium or potassium silicate, with at least 30% content of silicon atoms in the form Q ₂ and the form Q ₃ , in the form Q ₂ means that each silicon atom is involved in two bonds -Si-O-Si-, and the other two have terminal groups -Si-O-Si, where X is an alkali metal or H, and the form Q ₃ means that each silicon atom has three bonds -Si-O-Si-, and the remaining bond has a terminal group -Si-OX. 2. A structure according to claim 1, characterized in that it is an alkali metal, in particular sodium or potassium silicate, with at least 50% content of silicon atoms in the form Q ₂ and the form Q ₃ . Structural forming agent according to claim 1 or 2, characterized in that it is an aqueous solution of alkali metal, in particular sodium or potassium silicate, with a solids content of 10 to 60% by weight and a molar ratio of SiO ₂ : M ₂ O between 1.6 and 3.5. Structural forming agent according to claim 1 or 2, characterized in that it is an aqueous solution of alkali metal, in particular sodium or potassium silicate, with a solids content of 10 to 60% by weight and a molar ratio of SiO ₂ : M ₂ O between 1.6 and 3.5 adsorbed and / or absorbed on a silica-inert carrier such as the weight ratio of silica, expressed as dry matter: water bound to silica is from 100: 120 to 100: 40. Structural forming agent according to claim 4, characterized in that the carrier is 55 to 95% by weight of the solution to be applied, expressed as dry matter. 6. Structural forming agent according to claim 4 or 5, characterized in that the carrier is sodium carbonate, sodium sulfate, sodium borate, sodium perborate, sodium metallisicate or polysulfate such as trisodium sulfate or mixtures thereof. 7. A process for the preparation of a structure-forming agent according to any one of claims 4 to 6, characterized in that the concentrated aqueous solution of alkali metal silicate with a molar ratio of SiO ₂ : M ₂ O between 1.6 and 3.5 and content of a dry substance of from 10 to 60% by weight, is adsorbed and / or absorbed on an inorganic carrier, inert to silica, by contacting them, the carrier being such that the amount of silica bound water after adsorption and / or absorption to correspond to the weight ratio of silica, c DNase as dry matter: water associated with the silicate of 100: 120 to 100: 40. A method according to claim 7, characterized in that the contacting is carried out by spraying the concentrated aqueous silica solution onto the particulate carrier at a temperature between 20 and 95 ° C. 9. A method for producing spherical granules of hydrated alkali metal silicates and alkali metal carbonates, characterized in that an aqueous solution of alkali metal silicates containing at least 30% silicon atoms in Q ₂ form or Q ₃ form or a mixture of alkali metal silicates and carbonates are sprayed onto a rotating layer of alkali metal carbonate particles moving in a rotating granulation device, such as particle velocity, thickness of the rotating layer and flow rate of the spray solution are such that and the particle is converted into a plastic mantle or in contact with other particles, the resulting melt is compacted and dried to a silica bound water content corresponding to a silica weight ratio expressed as dry matter: water bound to silica from 100: 120 to 100: 40, as the form Q ₂ means. that each silicon atom is involved in two bonds -Si-O-Si- and the other two have terminal groups -Si-O-X, where X is an alkali metal or H, and the form Q ₃ means that each silicon atom has three the bonds are Si-0-Si-, and the other bond has an end group -Si-0-Χ. A method according to claim 9, characterized in that the aqueous solution of the alkali metal silicate or mixture of alkali metal silicate carbonate to be sprayed has a dry matter content of 30 to 55 wt%, the alkali metal silicate having a molar ratio of SiO ₂ : M ₂ O is between 1.6 and 3.5, and the amount of alkali metal carbonate present, optionally depending on the desired end product. A method according to claim 9 or 10, characterized in that the solution of the alkali metal silicate solution or mixture of alkali metal silicate and carbonate is sprayed at a temperature of 20 to 95 ° C. The method according to claims 9 to 11, characterized in that the particles forming the rotary layer of alkali metal carbonate have an average diameter between 10 and 150.10 ⁶ , a bulk weight without compaction of 0.4 to 1.1 g / cm ³ , water content from 0.05 to 0.4%, insoluble products from 5 to 100 mg / kg. A method according to any one of claims 9 to 12, characterized in that the particles forming the rotating layer contain less than 10% of the coated particles, except those of the alkali metal carbonate, with diameter and density close to that of the alkali metal carbonate particles. A method according to any one of claims 9 to 13, characterized in that the granulation device is a rotary granulator allowing the movement of the particles into a thin layer. 15. The method of claim 14, wherein the rotary granulator is a dragee. The method according to claims 9 to 13, characterized in that the granulating device is a drum. A method according to claims 9 to 16, characterized in that the carbonate particles move at a temperature between 15 and 200 ° C. 18. The method according to claims 9 to 17, characterized in that the amount of silica solutions or 5 mixtures of silicate and carbonate dispersed and the carbonate particles used corresponds to a liquid flow rate: particle flow rate of 0.2 to 0.8 L / kg, these values being expressed as sodium salts. 10 The method according to claims 9 to 18, characterized in that the compaction is carried out at room temperature by rotating the granules obtained during the granulation step in a rotary device. 15 20. A method according to claim 19, wherein the sealing is carried out in a rotating drum. 21. The method according to claims 9 to 20, characterized in that the granules obtained after compaction are dried in a fluidized bed. A method according to claims 9 to 21, characterized in that small amounts of the liquid compounds commonly used in the detergents are added to the granules obtained after drying. 23. Spherical granules of alkali metal silicates and alkali metal carbonates, characterized in that they contain from 8 to 38 30% by weight of silicate with a molar ratio of SiO ₂ : M ₂ O between 1.6 and 3.5, carbonate from 47 to 48% by weight, water from 5 to 25% by weight and have a bulk weight without compaction of 0.7 to 1.5 g / cm ³ , average diameter of 0.4 to 1.8 mm, with a standard deviation of 35 log, ₀ in the range of 0.02 to 0.3, with the weight ratio of silica expressed as dry matter: water bound to silica being from 100: 120 to 100: 40. 24. Spherical granules of hydrated sodium silicate and sodium carbonate, characterized in that they contain from 24 to 31 wt.% Silicate with a molar ratio of SiO ₂ : M ₂ O between 1.8 and 2.6, carbonate from 64 to 69% by weight, water from 12 to 20% by weight and having a bulk weight without compaction of 0.7 to 1.5 g / cm ³ , preferably 0.8 to 1 g / cm ³ , average diameter of 0, 4 to 0.8 mm, with a standard deviation of log ₁₀ of the order of 0.05 to 0.1, a rate of less than 2 min for a 90% dissolution in water and less than 4 min for a 95% dissolution in water, such as the weight ratio of silica, expressed as dryness in coarser: water associated with the silicate is from 100: 120 to 100: 40. 25. The use of a structure-forming agent according to claim 3 for adding in detergent powder compositions by spraying on the main laundry mixture or on mixtures of substances with laundry properties, in a weight ratio of silicate: powder or laundry mixture between 1: 100 to 30: 100 and a weight ratio of silicate : silica bound water between 100: 120 and 100: 40. 26. Use of a structure forming agent according to any one of claims 4 to 8 and 25 for powder detergent compositions for dishwashers with a silica content of 3 to 90% by weight of the dry matter relative to the composition. Use of a structure forming agent according to any one of claims 4 to 8 and 25 for powder detergent compositions for washing machines with a silica content of 3 to 60% by weight of the dry matter relative to the composition.