RU2097411C1 - Modifying additive for detergent composition, method for its production, spherical cogranules, method for their production and detergent composition - Google Patents

Abstract

FIELD: production of detergent composition. SUBSTANCE: modifying additive comprises 55-95 mass of carrier and aqueous solution of silicate of alkaline metal. Said carrier is chemically inert in respect with silicate and is different from sodium tripolyphosphate. Said silicate is product of absorption of aqueous solution having 10-60 % of dry extract, molar ratio SiO₂: M₂O in it being 1.6-3.5. EFFECT: improved quality of desired product. 20 cl, 5 tbl

Description

The invention relates to a modifying additive. The subject of the invention is a modifying additive formed by alkali metal silicates, enriched in structures in which silicon atoms are in the forms of Q ₂ and Q ₃ , said additive being intended for detergent compositions, in particular for washing powders, especially for washing or dishwashers.

 By “modifying additive” is meant any active additive that improves the properties of the surfactants of the detergent composition.

 It is necessary that the modifying additive has an effect called "softening" of the water used for washing (washing). Therefore, it must remove calcium and magnesium, which are present in water in the form of soluble salts, and in the contaminants of linen in the form of complex forms, more or less soluble. Removal of calcium and magnesium can be carried out either by complexation in the form of soluble structures, or by ion exchange, or by precipitation. When it comes to deposition, the latter should be controlled to avoid scale formation on the laundry or on the elements of washing machines.

 This control of precipitation is achieved, in particular, due to water-soluble polymers having an affinity for calcium and magnesium.

 It is also necessary that the modifying additive gives the emulsifying effect of surfactants with respect to fatty contaminants and also the dispersing effect with respect to "pigment" contaminants, such as metal oxides, clays, silica, various dusts, humus, limestone, soot, etc. .d.

 This dispersing effect is usually achieved due to the presence of polyanions, which create a high density of negative charges on the interface.

 It is also necessary that the modifying additive creates an ionic strength favorable for the action of surfactants, in particular by increasing the size of the micelles.

It is also necessary that it creates OH ions ^- for saponification of fats, and also to increase negative surface charges on the textile surface and on the particles of impurities.

 Silicates have long been regarded as good detergent additives, but at present they are little used in phosphate-free laundry detergents.

The most commonly used silicates for this application are those having a molar ratio of SiO ₂ / Na ₂ O comprised between 1.6 and 2.4. They are either commercially available or in the form of concentrated solutions with a solids concentration of about 35-45 wt. or in the form of a fine powder of silicate, if necessary, compressed.

 Commercial concentrated solutions are most often prepared on the basis of a completely amorphous silicate called “glassy” as well as “liquid (soluble) glass”.

These liquid glasses are dissolved in water in an autoclave under pressure at a temperature of 140 ^o C. Thus obtained commercial solutions having about 45 wt. dry residue for silicate with a ratio of 2 and about 35 wt. for silicate with a ratio of 3.5.

 Concentrated silicate solutions using a device for creating a detergent solution are introduced into an aqueous suspension containing other components of the detergent solution. The suspension is then spray dried. The silicate, sprayed and dried together with other components, then contains no more than 20% of the associated water in relation to its dry weight, and even less.

 As for commercial powdered silicate, it is obtained by drying by spraying concentrated solutions of glassy silicate; it is necessary to save from 20 to 22 wt. water relative to the final product to ensure good solubility of the specified product.

 It was found that when it dissolves in a washing solution in a ratio of 1 to 3 g / l, this powdery silicate, which contains only 20 to 22 wt. associated water (relative to the final product), has only weak modifying properties.

Indeed, this powdered silicate, converted into a solution, forms mainly monomeric silicon structures with the formula Si (OX) ₄ , where X represents H or Na, which do not have a modifying effect. Such monomeric structures can be re-associated with each other with the formation of polyanions only if the concentration of silicate is at least 50 to 500 g / l, and then slowly.

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

 Everything that has been established for a powder containing 20 to 22% chemically associated water (relative to the final product) is also valid for formulations containing silicate with 20% associated water (relative to dry silicate), which are prepared by introducing a concentrated silicate solution in suspension, followed by drying.

The applicant firm found that when the alkali metal silicate is rich in structures in which the silicon atoms are in the form of Q ₂ and Q ₃ , then the polyanionic structures formed by dilution to concentrations from 1 to 3 g / l in a washing medium, have a life expectancy sufficient to allow them to play the role of a “modifying additive” with a washing action.

The expression "silicon atoms in the form of Q ₂ and Q ₃ " is a representation of the degree of association of silicon atoms with each other; “Q ₂ ” means that each silicon atom participates in two —Si — O — Si— bonds, the two remaining bonds being at the —Si — OX end groups, where X is an alkali metal or H; Q ₃ means that each silicon atom participates in three —Si — O — Si— bonds, with the remaining bond being at the —Si — OX end group.

The modifier for the detergent composition of the invention is characterized in that it is formed by an alkali metal silicate, in particular sodium or potassium, containing at least 30%, preferably 50%, of silicon atoms in the form of Q ₂ and Q ₃ .

The specified silicate may have a molar ratio of SiO ₂ / M ₂ O. of the order of from 1.6 to 3.5, preferably of the order of from 1.8 to 2.6.

 The specified modifying additive may be in any structured (powder, granules, etc.) or unstructured form.

The first embodiment of the invention is a modifying additive consisting of an aqueous solution with a concentration on a dry residue of about 10-60 wt. preferably about 35-50 wt. alkali metal silicate, in particular sodium or potassium, with a molar ratio of SiO ₂ / M ₂ O of the order of from 1.6 to 3.5, preferably of the order of from 1.8 to 2.6.

A concentrated alkali metal silicate solution, used as a modifying additive, is preferably obtained by dissolving "water glasses" in water in an autoclave under pressure at a temperature of 140 ^o C followed by possible dilution; it can also be obtained using other known methods, such as the direct action of caustic soda on sand in a concentrated solution of the first.

As a result of analysis by NMR, it was found that:
a solution with 45% solids of glassy silicate with a molar ratio of SiO ₂ / Na ₂ O 2 contains 34% of structures Q ₃ , 51% of structures Q ₂ , 12% of structures Q ₁ and 3% of structures Q ₀ ;
a solution with 35% solids with a ratio of 3.5 contains 46% structures Q ₂ , 27% structures Q ₂ , 16% structures Q ₄ , 9% structures Q ₁ and 2% structures Q ₀ .

 The specified solution as a modifying additive can be used after adding by spraying to the washing powder from the "bottom of the column" in the presence of a spraying unit or to a mixture of components of the washing formulation in the case of dry mixing, and all this is within the adsorption capacity of the powders. The resulting powdery mixture can, if necessary, be moderately dried, so that the dry silicate / water weight ratio remaining associated with the silicate is between 100/120 and 100/40, preferably between 100/90 and 100/50.

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

Another embodiment of the invention is that an aqueous solution with a solids concentration of about 10-60 wt. preferably about 35-50 wt. alkali metal silicate, in particular sodium or potassium, with a molar ratio of SiO ₂ / M _{2 of the} order of 1.6 to 3.5, preferably of the order of 1.8 to 2.6, is adsorbed and / or adsorbed on a carrier in the form of particles, inert with respect to the silicate, the weight ratio of silicate (calculated on the dry residue) / water remaining associated with the silicate varies from 100/120 to 100/40, preferably from 100/90 to 100/50. "Inert" means chemically inert.

 By water "associated" with silicate is meant water from a solution deposited on a carrier that cannot be combined with a mineral carrier, in particular in the form of crystallization hydrate.

 Among the inorganic carriers for the silicate solution, it is possible to mention compounds, preferably water-soluble, such as sodium carbonate, sodium sulfate, sodium borate, sodium perborate, sodium metasilicate, phosphates or polyphosphates, such as trisodium phosphate, sodium tripolyphosphate, etc. moreover, these carriers are in pure form or in a mixture with each other.

 The carrier is usually about 55 to 95 wt. preferably of the order of from 65 to 85 wt. from the applied solution calculated on the dry matter (i.e., the weight of the solution calculated on the dry residue + weight of the carrier).

The specified solution on the carrier can be prepared by adsorption and / or absorption by contacting a concentrated aqueous solution of alkali metal silicate with a molar ratio of SiO ₂ / M ₂ O of the order of 1.6 to 3.5, preferably of the order of 1.8 to 2 , 6, containing a dry residue of the order of 10 to 60 wt. preferably of the order of from 35 to 50 wt. with an inorganic carrier inert with respect to the silicate, said carrier being present in such an amount that the amount of water remaining associated with the specified silicate after adsorption and / or adsorption corresponds to the weight ratio silicate (calculated on the dry residue) / water associated with silicate, of the order of 100/120 to 100/140, preferably of the order of 100/90 to 100/50.

The contacting operation can be carried out by adding, in particular by spraying, the specified concentrated silicate solution to the carrier in the form of particles in any known mixer with high efficiency, in particular, of the LODIGE ^® type or in granulation devices (drum, plate, etc. .) etc. at a temperature of the order of from 20 to 95 ^o C, preferably of the order of from 70 to 95 ^o C.

 Carriers that can be used are those already mentioned in the listing.

 The amount and concentration of the silicate solution used are a function of the absorbent and / or absorbent capacity of the support, given the likely possibility for the support to form, in particular crystallizable hydrates; the content of water not associated with silicate, which may be in the form of a hydrate in the carrier, can be determined by a known method by differential thermal analysis or by quantitative X-diffraction. Water combined with a carrier, possibly in the form of other forms other than these hydrates, can be determined using appropriate physicochemical methods (thermoporosimetry, thermogravimetry, proton NMR, IR).

 The limit of absorbent and / or absorbent capacity of the specified carrier can be determined in accordance with known methods, for example, by measuring the change in angle based on the angle of repose (collapse) depending on the content of the silicate solution additive.

 If necessary, the mixture formed by the carrier and the silicate solution can itself be dried, but in a moderate manner, so as to obtain the desired proportion of water associated with the silicate.

 The obtained particles deposited on a carrier of a silicate solution can be ground, if desired, so as to obtain an average diameter of the order of 200 to 800 microns.

 Solutions of alkali metal silicate in the form adsorbed and / or absorbed on an alkali metal carbonate, which are in the form of spherical granules together with hydrated alkali metal silicate and alkali metal carbonate, are modifying additives of the invention.

These joint spherical granules with hydrated alkali metal silicates and alkali metal carbonates can be obtained in accordance with a method characterized in that:
an aqueous solution based on alkali metal silicates or based on a mixture of alkali metal silicates and carbonates is sprayed onto a moving bed of particles based on alkali metal carbonates entering a rotary granulating device, the particle velocity, the thickness of the moving bed and the flow rate of the sprayed solution being such that each particle would turn into a joint plastic granule in contact with other particles;
subjecting the obtained granules to operations to increase density;
drying said granules with increased density to obtain a water content associated with silicate, which corresponds to the weight ratio of silicate (calculated on the dry residue) / water associated with silicate, of the order of 100/120 to 100/40.

 Among the silicates and carbonates of alkali metals, preferably sodium and potassium silicates and carbonates can be mentioned, and especially silicates and sodium carbonates.

An aqueous solution based on silicate or on the basis of a mixture of silicate / carbonate, which is atomized, can have a solids content of the order of 30 to 55 wt. preferably from 30 to 45 wt. said alkali metal silicate has a molar ratio of SiO ₂ / M ₂ O of the order of 1.6 to 3.5, preferably of the order of 1.8 to 2.6, and especially close to 2; said carbonate may, if necessary, be present with a content defined as a function of the final desired product, depending on the proportions.

A silicate-based solution or a silicate / carbonate-based solution is pulverized at a temperature of the order of 20 to 95 ^° C, preferably of the order of 70 to 95 ^° C, the introduction of compressed air (for example, using a bifunctional nozzle) at a temperature of same order.

The particles used to produce the joint granules consist mainly of alkali metal carbonate and have:
an average diameter of the order of 10 to 150 microns, preferably of the order of 20 to 100 microns, and especially close to 30-80 microns,
bulk density without ramming (not mass density) of the order of from 0.4 to 1.1 g / cm ³ , preferably of the order of from 0.6 to 1.1 g / cm ³ ;
water content of the order of from 0.05 to 0.4 wt. preferably of the order of from 0.1 to 0.3 wt.

 the content of insoluble matters is of the order of 5 to 100 mg / kg, usually of the order of 10 to 60 mg / kg.

 Modified or conventional carbonate grades may be used.

 Along with this, carbonate particles may be present in small amounts (less than 10 wt. From the joint granules) other particles, such as anti-precipitating polymers (carboxymethyl cellulose, etc.), enzymes, etc. commonly used in the field of detergents that have a diameter and density close to those of carbonate particles.

 The device used to carry out the joint granulation operation by atomization can be any rotary device such as a rotating plate, dragee making machine, rotating drum, granulator mixer, etc.

A first preferred embodiment of these joint granules is to use a rotary granulator to provide particles in the form of a thin layer. Dragee-making machines having an axis of rotation deflected relative to the horizontal axis by an angle exceeding 20 ^° , preferably exceeding 40 ^° , are particularly suitable; their geometry can be very different: in the form of a truncated cone, flat, in the form of a ladder, a combination of these three forms, etc.

A second preferred embodiment of these joint granules is to use a rotary drum whose deflection angle is at least 3% and preferably at least 5%
Particles based on carbonate move at a temperature of the order of 15 to 200 ^o C, preferably of the order of 15 to 120 ^o C and especially of the order of 15 to 30 ^o C.

 The pulverizable amounts of a silicate-based solution or based on a silicate / carbonate mixture and the number of carbonate-based particles to be used correspond to a liquid flow rate / particle flow rate, which can vary from 0.2 to 0.8 l / kg, preferably from 0, 4 to 0.7 l / kg and especially from 0.62 to 0.7 l / kg, and these values are expressed in terms of sodium salts.

 The flow rate of the sprayed solution, the speed of movement of the particles, as well as the thickness of the layer of moving particles are such that each particle absorbs the liquid and sticks to the other particles with which it is in contact, in order to obtain plastic granules, and not a pasty substance.

 The speed of movement of the particles and the thickness of the layer are controlled by the speed of introduction of particles into the device for granulation and its characteristics.

 The residence time of the particles in a plate or drum type device is usually on the order of 15 to 40 minutes.

According to the raw material, the specialist can adapt the characteristics of the device used to the desired product, namely:
for dragee making machine:
its geometry (in the form of a truncated cone, flat, staircase or a combination of these three forms);
its size (depth, diameter);
its deflection angle;
its rotation speed;
relative locations of solids and liquids feed elements;
for drum:
its geometry (pipe diameter);
its deflection angle;
its rotation speed;
pipe loading;
relative locations of solids and liquids feed elements.

The resulting unconsolidated and not dried joint granules have characteristics determined by the conditions used for granulating. They usually have:
silicate content of the order of from 7 to 30 wt. preferably about II to 23 wt. and especially about 21 to 23 wt.

 the carbonate content of the order of 41 to 75 wt. preferably of the order of from 48 to 64 wt. and especially about 48 to 51 wt.

 a water content of the order of from 18 to 29%, preferably of the order of 25 to 29 wt. and especially about 27 to 29 wt.

 The operation of increasing the density can be carried out at ambient temperature by rolling the joint granules obtained in the granulation stage in a rotary device.

 This device is preferably independent of the granulation device.

 This stage of increasing the density can mainly be carried out by introducing and staying the joint granules in the rotary drum. The deflection angle of the latter is at least 3%, preferably at least 5%. The dimensions of this drum, its rotation speed and the residence time of the joint granules are a function of the desired density; the residence time is usually on the order of 20 minutes to 3 hours, preferably on the order of 20 to 90 minutes.

 Granulator mixers are also well suited for this density increasing operation.

 Joint granulation and density increase operations can also be carried out in the same device, for example, in a ladder machine for the manufacture of dragees, wherein an increase in the density of joint granules is achieved by rolling said joint granules on the last steps of the device; in addition, these two operations can be carried out in a two-section drum.

Then the joint granules with high density are dried using any known method. A very effective method is fluidized bed drying using an air stream at a temperature of the order of 30 to 90 ^o C, preferably 60 to 80 ^o C. This operation is carried out for a duration depending on the air temperature, on the water content in the joint granules at the exit from the device for granulation and from the desired content of the dried joint granules, as well as from the conditions of the fluidized bed; the specialist will be able to adapt these various conditions to the desired product.

Dried dense joint granules are usually:
silicate content of the order of from 8 to 38 wt. preferably of the order of from 14 to 31 wt. and especially about 24 to 31 wt.

 the carbonate content of the order of from 47 to 87 wt. preferably of the order of from 59 to 81 wt. especially about 64 to 69 wt.

 water content of the order of 5 to 25 wt. preferably of the order of from 7 to 20 wt. and especially from 12 to 20 wt.

bulk density without ramming of the order of from 0.7 to 1.5 g / cm ³ , preferably of the order of from 0.75 to 1.5 g / cm ³ , and especially of the order of from 0.8 to 1 g / cm ³ ;
the average diameter (in the sense of the total percentage of transmitted particles) of the order of from 0.4 to 1.8 mm, preferably of the order of 0.6 to 0.8 mm, with a deviation of the log ₁₀ type from 0.02 to 0.3, preferably from 0.05 to 0.1.

 These stages: joint granulation increase in drying density - allow to obtain joint granules based on hydrated alkali metal silicates and alkali metal carbonates, which are completely spherical, dense and rapidly soluble in water.

Spherical joint granules based on hydrated sodium silicates and sodium carbonate, especially adapted for the preparation of detergent compositions for dishwashers and washing machines, are granules having the following characteristics:
silicate content of the order of from 24 to 31 wt.

 carbonate content of the order of 64 to 69 wt.

water content from 12 to 20 weight%
bulk density without ramming of the order of from 0.7 to 1.5 g / cm ³ , preferably of the order of from 0.8 to 1 g / cm ³ ;
an average diameter of about 0.4 to 0.8 mm with a log ₁₀ deviation of 0.05 to 0.1;
dissolution rate of 90% in water for less than 2 minutes and 95% for less than 4 minutes.

The dissolution rate of 90% or 95% in water is understood to mean the time required to dissolve 90% or 95% of the product with a concentration of 35 g / l in water at 20 ^o C.

 When it is structured (powder, joint granules, etc.), the modifying additive according to the invention is used in detergent compositions for dishwashers with a content of from 3 to 90 wt. preferably from 3 to 70 wt. from said compositions; the amounts used in the compositions for washing machines range from 3 to 60 wt. preferably of the order of from 3 to 40 wt. from the specified composition (these amounts are expressed by the weight of dry silicate relative to the weight of the composition).

 In addition to the modifying additive constituting the subject of the invention, at least one surfactant is present in the detergent composition in an amount that can vary from 8 to 20%, preferably of the order of 10 to 15 wt. from the specified composition.

Among these surfactants, you can specify:
anionic surfactants such as alkali metal soaps (alkali metal salts of fatty acids C ₈ -C ₂₄ ), alkali metal sulfonates (alkyl benzene sulfonates C ₈ -C ₁₃ , alkyl sulfonates C ₁₂ -C ₁₆ ), ethoxylated and sulfated fatty alcohols C ₆ - C ₁₆ , ethoxylated and sulfated alkyl phenols C ₈ -C ₁₃ , alkali metal sulfosuccinates (C ₁₂ -C ₁₆ alkyl sulfosuccinates), etc.

nonionic surfactants such as C ₆ -C ₁₂ polyoxyethylated alkyl phenols, C ₈ -C ₂₂ hydroxyethylated aliphatic alcohols, block copolymers of ethylene oxide and propylene oxide, carboxylic acid amides, optionally polyoxyethylated;
amphoteric surfactants such as alkyl dimethyl betaines;
cationic surfactants such as alkyltrimethylammonium chlorides or bromides, alkyl dimethylethylammonium.

Among other things, various components may be present in the detergent composition, for example, such as:
modifying additives such as:
phosphates containing at least 25 wt. from the whole composition;
zeolites up to about 40 wt. from the whole composition;
sodium carbonate up to about 80 wt. from the whole composition;
nitrile acetic acid up to about 10 wt. from the whole composition;
citric acid, tartaric acid up to about 20 wt. from the whole composition;
moreover, the total amount of modifying additives corresponds to from about 0.2 to 80%, preferably from 20 to 45 wt. from all of the specified detergent composition;
whitening substances such as perborates, percarbonates, chlorisocyanurates, N, N, N ', N'-tetraacetylethylenediamine (TAED) up to about 30 wt. from all of the specified detergent composition;
antioxidants such as carboxymethyl cellulose, methyl cellulose in amounts that can reach up to about 5 wt. from all of the specified detergent composition;
substances that prevent the formation of scale, such as copolymers of acrylic acid and maleic anhydride in amounts that can reach about 10 wt. from all of the specified detergent composition;
fillers such as sodium sulfate for powdered detergents in an amount that can reach up to 50 wt. from all of the specified detergent composition.

 The following examples are given as illustrative and cannot be construed as limiting the scope and meaning of the invention.

Examples 1 5. Properties of a modifying additive based on:
a solution of sodium silicate with a molar ratio of SiO ₂ / Na ₂ O 2 with 45 wt. dry residue (example 2);
a solution of sodium silicate with a molar ratio of SiO ₂ / Na ₂ O of 3.4 with 35 wt. dry residue (example 4);
determined by a THERMOTOMETER (US Testing Company, Hoboken, USA) in a binary mixture with anionic surfactant LABS (linear sodium dodecylbenzenesulfonate from ALDRICH), and reflectance measurements are carried out using a GARDNER reflectometer.

These characteristics are compared with the characteristics of:
one LABS with a concentration of 2 g / l (example 1);
finely divided silicate powder with a ratio of 2 containing 22% water (i.e. 28.2% water relative to dry silicate) (example 3);
finely divided silicate powder with a ratio of 3.4 containing 18.6% water (i.e. 22.8% water relative to dry silicate) (Example 5);
which are used under the same conditions (4 g / l).

 The results of these measurements are given in table. one.

Method of measurement
Principle. A simplified machine wash is simulated in a tergotometer, washing samples from standardized contaminated tissues using a surfactant and a test modifier at a temperature of 65 ^° C. The wash lasts 20 minutes, and the color of the fabrics is determined before and after washing. Achieve “white color” by erasing the same type of samples with a single surfactant to evaluate the value of the test modifier.

Experimental technique
The thermotometer is a device consisting of 4 chambers with a capacity of 2 l each made of stainless steel, on which pulsators are installed, which are regulated at 100 cycles / min. The cameras are placed in a tank of water, the temperature of which is regulated at 65 ^o C.

1. In each chamber is placed 1 liter of hard water from a water tap (34 ^o hardness on a French scale). After heating the water, enter:
5 samples of size 10x12 cm white cotton brand 405W company TEST FABRIC,
5 samples of 10x12 cm in size of polyester cotton (PEC) of white color according to the standard N 7435 of TEST FABRIC firm,
2 samples of 10x12 cm cotton contaminated with EMPA (a mixture of carcass and olive oil), article 101 from GALLEN;
2 samples of 10x12 cm cotton contaminated with red wine, article 114 from GALLEN;
2 samples of 10x12 cm polyester cotton (PEC) contaminated with EMPA, article 104 from GALLEN.

2. At the same time carry out 3 of the following operations:
inclusion of a chronometer;
stirring start;
addition of a mixture: modifier / surfactant.

 The modifying additive is tested at a concentration of 4 g / l (weight calculated on the dry matter of the product), and 2 g / l of LABS is added to it.

3. Rinse
After 20 minutes, wash the water and rinse the fabric with 3x1 L of cold water from a faucet.

4. Squeezing and drying
Squeeze the samples, pre-dried them, laying them individually on absorbent paper. Then the fabric is twice passed through a rasping machine between two sheets of absorbent paper at a temperature of approximately 110 ^o C.

5. color measurement
Standardize the GARDNER instrument by measuring zero on a black plate designed for this purpose, then by measuring the values of L, a, b on a standard white plate of the same type as the black one.

The value of L characterizes the color in shades from white to black:
L 100 corresponds to a white sample;
L 0 corresponds to the black pattern.

The value of a characterizes the color in shades from green to red:
a> 0 color tends to red;
and <0, the color tends to green.

The value b characterizes the color in shades from yellow to blue:
b> 0 color tends to yellow;
b <0 color tends to blue.

 After standardization, the actual measurements are carried out. 2 samples from each tissue category are taken from the chamber, 5 measurements are taken with the sample (i.e., one in the center and one in the four corners), placing a heavy metal plate on the fabric, and then the arithmetic average of 10 determinations is determined. Do the same with non-washed fabrics.

6. Processing of results
DL and DE are calculated for each experiment and for each type of tissue.

Рассчитывают среднее значение из DL и DE для каждого продукта и для каждого типа загрязненной ткани.DL L (after washing) L (before washing);
Da a (before washing) a (after washing);
Db b (before washing) b (after washing);

Calculate the average of DL and DE for each product and for each type of contaminated tissue.

Then for each product calculate:
detergent against cotton contaminated with EMPA DE medium cotton EMPA,
the washing ability in relation to the PEC contaminated with EMPB DE average PEM EMPA;
washing ability in relation to cotton contaminated with wine DE medium cotton VIN;
total washing ability is the sum of washing abilities of cotton EMPA, PEM EMRA, cotton WINE.

Examples 6 and 7. Load into an LODIGE M5G ^® mixer (commercially available from LODIGE) 800 g of anhydrous tripolyphosphate H $\genfrac{}{}{0ex}{}{\text{®}}{}$$\genfrac{}{}{0ex}{}{}{\text{2}}$ commercially available from RHONE-POUL ENC.

After closing and putting the device into rotation at a speed of 400 rpm, 200 g of sodium silicate solution with a molar ratio of SiO ₂ / Na ₂ O 2 with 45% solids are introduced by spraying.

 This introduction lasts 10 minutes, after an additional 10 minutes of mixing, the product is removed by rotation, which is left alone for 2 hours on a flat surface under open air and at ambient temperature.

Product Features are:
the content of partially hydrated tripolyphosphate (TPF): 82 wt.

 sodium silicate content: 9 wt.

silicate associated water content: 9 wt. those. 100% relative to dry silicate;
The total amount of water contained in the product is determined by measuring the weight loss of the latter when heated to 500 ^° C; on the other hand, the amount of water bound in the form of hydrates is measured by differential thermal analysis. The amount of associated water is calculated as the difference between total water and water bound as a hydrate.

 average diameter of 250 microns.

 The characteristics of the modifying additive in this product are measured in accordance with the method described above, however, replacing 2 samples of PEC contaminated with EMPA, article 104 with 2 samples of cotton contaminated with WFK, KREFELD company with the same dimensions (example 6).

These characteristics are compared with the characteristics of the mixture of powders of anhydrous TPF H $\genfrac{}{}{0ex}{}{\text{®}}{}$$\genfrac{}{}{0ex}{}{}{\text{2}}$ and finely divided silicate with a SiO ₂ / Na ₂ O 2 ratio with 22% water at a TPF / dry silicate weight ratio of 800/90, all under the same conditions (4 g / l) Example 7.

 The measurement results are given in table. 2.

Example 8. The granulation system consists of a flat plate with a diameter of 800 mm and a depth of 100 mm. During the granulation, the rotation speed is about 35 rpm, and the deviation of the axis of rotation relative to the horizontal axis is about 55 ^o . A powder consisting of finely divided particles of sodium carbonate, the main characteristics of which are as follows, is continuously fed to a granulation plate at a flow rate of 21.4 kg / h.
alkalinity 99.61%
the water content of 0.12 wt.

bulk density without ramming 0.56 g / cm ³ ;
average diameter 95 microns;
insoluble matter content 58 mg / kg.

This powder, rotated in a granulation plate, is sprayed with air at a temperature of 80 ^o C a solution of sodium silicate with a flow rate of 13.4 l / h at a temperature of 80 ^o C through a bifunctional nozzle located at a distance of 20 cm from the bottom of the machine for making dragees. The content of the active substance and the molar ratio of SiO ₂ / Na ₂ ) of the atomized solution are respectively 43 wt. and 2.

 The average residence time of a particle in a plate is about 10 to 15 minutes. The temperature of the particles leaving the tray is the ambient temperature.

 The granules leaving the plate are introduced into a rotating tube with smooth walls with a diameter of 500 mm, a length of 1300 mm and having a deviation of the order of 5%. The output aperture is set so that the average particle residence time is approximately 40 minutes. The rotational speed of the drum (18 rpm) is selected so as to have a rolling layer of particles, which favors an increase in the density of these particles.

The granules thus obtained are dried in a fluidized bed at a temperature of about 80 ^° C. (air temperature for creating a fluidized bed is 86-90 ^° C.) for 10 to 15 minutes.

The product thus dried has the following characteristics:
carbonate content 65 wt.

 silicate content 21 ± 0.5 wt.

 water content 13.5 wt.

bulk density without tamping 0.90 g / cm ³ ;
residues with a size of 1 mm 10.8 wt.

average diameter 0.73 mm;
past particles with a size of 0.2 mm 6 wt.

90 wt. the product is dissolved in 50 s (aqueous solution with a concentration of 35 g / l at 20 ^o C,
95 wt. the product dissolves in 65 s (aqueous solution with a concentration of 35 g / l at 20 ^o C),
whiteness L 96.3;
abrasion resistance 7%
The granules have excellent storage stability.

Abrasion Resistance Measurement
Equipment:
A fluorometer is used, a standard device used to characterize hydraulic binders, which is described in French standard P 15-443.

Experimental technique:
Sift 50 g of product between sieves with mesh sizes of 1200 and 180 μm using a ROTO-LAB ^® laboratory sieving machine (sold by PROL ABO).

 Remove part enclosed between 180 and 1200 microns.

 Weigh approximately 25 g of test product accurately; let M be the exact mass.

 Put this mass in the meter.

Weigh the filter type Soxhlet ^® (marketed by PROL ABO) is empty and dry, and put it into the upper part of the pipe to create the fluidized bed; let M1 be its mass.

 Create a fluidized bed for 5 min (dry air flow: 15 l / min).

 Remove the entrained product along with the filter, as well as finely divided fines that have settled down, possibly on the vertical walls of the pipe to create a fluidized bed, using a brush (banner) of the appropriate diameter. Weigh: let M2 be the mass of this little thing and filter.

Sift the residue from the bottom of the pipe onto the ROTO-LAB ^® again to create a fluidized bed and remove fines with dimensions smaller than 180 microns for weighing; let MZ be the mass of this little thing.

Payment. Expression of results:
The degree of abrasion is equal to the percentage of fines with a size of less than 180 microns formed during the residence time of this product in a fluidized bed.

Пример 9. Повторяют операции, описанные в примере 8, привнося в них только следующие изменения:
тарелка для гранулирования скорость вращения 30 об/мин;
подача порошка: 22 кг/ч;
подача силикатного раствора: 13 л/ч.

Example 9. Repeat the operations described in example 8, making them only the following changes:
plate for granulation rotation speed 30 rpm;
powder supply: 22 kg / h;
silicate solution supply: 13 l / h.

Density increase:
drum rotation speed: 10 rpm

Fluidized bed drying:
temperature 90 ^o C;
duration: 20 minutes

The dried product has the following characteristics:
the carbonate content of 60.9 wt.

 silicate content 22.9 ± 0.5 wt.

 water content 16.1 wt.

bulk charge without ramming 0.86 g / cm ³ ;
residues with a size of 1 mm 2.6 wt.

average diameter 0.64 mm;
past particles with a size of 0.2 mm 7.3 wt.

90 wt. the product dissolves in 75 s (aqueous solution with a concentration of 35 g / l at 20 ^o C);
95 wt. the product dissolves in 102 s (aqueous solution with a concentration of 35 g / l at 20 ^o C);
whiteness L 95.6;
abrasion resistance: 9.2%
The granules have excellent storage stability.

 Example 10. The granulation system consists of a drum rotating at a speed of 40 rpm, with smooth walls with a diameter of 500 mm, a length of 1300 mm, which has a deviation of the order of 7.5%. The output aperture is set so that the average particle residence time is would be about 15 to 20 minutes.

 A carbonate powder having the same characteristics as the powder of Examples 1 and 2 is continuously fed into the drum at a flow rate of 37 kg / h.

This powder, driven into rotation in a drum, is sprayed with air at a temperature of 80 ^o C through a bifunctional nozzle with a flat nozzle located in the first third of the drum, a silicate solution (having an active substance content of 45.6 wt. And a weight ratio of SiO ₂ / Na ₂ O 2) at a temperature of 80 ^o C with a flow rate of 18 l / h.

Joint granules at the outlet of the drum are at ambient temperature and have a density of 0.68 g / cm ³ .

Then, an increase in the density of the joint granules is carried out periodically for 1 hour in a rotating drum with smooth walls with a diameter of 500 mm, a length of 1300 mm, which has a deviation of 5%
The rotational speed of the drum is 20 rpm.

Thus obtained granules are dried in a fluidized bed at a temperature of about 65 ^o C (air temperature to create a fluidized bed is 70 ^o C) for 15 minutes

The dried product has the following characteristics:
carbonate content 62 wt.

 silicate content 20.5 ± 0.5 wt.

 the water content of 17.6 wt.

bulk density without ramming of 0.820 g / cm ³ ;
residues with a size of 1 mm 5 wt.

average diameter 0.65 mm;
past particles with a size of 0.2 mm 0.6 wt.

90 wt. the product dissolves in 50 s (aqueous solution with a concentration of 35 g / l at 20 ^o C);
95 wt. the product is dissolved in 63 s (aqueous solution with a concentration of 35 g / l at 20 ^o C).

 The granules have excellent storage stability.

Example 11. Repeat the operations described in example 3, making them only the following change:
Density increase:
in periodic mode for 2 hours

The dried product has the following characteristics:
the carbonate content of 60.8 wt.

 silicate content 19.3 ± 0.5 wt.

 the water content of 19.9 wt.

bulk density without tamping 0.91 g / cm ³ ;
residues with a size of 1 mm 1.6 wt.

average diameter 0.57 mm;
past particles with a size of 0.2 mm 1.22 wt.

90 wt. the product dissolves in 37 s (aqueous solution with a concentration of 35 g / l at 20 ^o C),
95 wt. the product is dissolved in 45 s (aqueous solution with a concentration of 35 g / l at 20 ^o C).

 The granules have excellent storage stability.

 Examples 12 and 13. The advantages of the modifying additive in the form of joint granules from example 8 are determined in accordance with the method described in examples 1 to 5.

They are compared with the advantages of a mixture of sodium carbonate powder and finely ground sodium silicate powder with a SiO ₂ / Na ₂ O 2 ratio containing 22% water in the final product (i.e. 28.2% water relative to dry silicate) with a weight ratio of 3 / 1 (carbonate / R ₂ , finely divided).

 The results are shown in table. 3. Amounts of carbonate and silicate are expressed as dry matter.

 The results with co-granules have been found to be better than those with a powder mixture having the same silicate / carbonate ratio.

Example 14. In the mixer LODIGE M5G ^® in accordance with the experimental method of examples 6 and 7, particles are prepared based on:
1800 g of light powdered sodium carbonate having an average particle diameter of about 110 microns;
1200 g of sodium silicate solution with a molar ratio of SiO ₂ / Na ₂ O of 3.4 with 37% solids.

After adding a silicate solution over 5 minutes, after an additional 5 minutes of stirring and staying in the open air for 2 hours at ambient temperature, a product is recovered that has the following characteristics:
the content of sodium carbonate 60 wt.

 silicate content of 20 wt.

the water content associated with silicate, 20 wt. (i.e. 100% relative to dry silicate);
average diameter of 400 microns.

 This product is introduced by dry mixing with additives to obtain the following composition for a washing machine.

The composition of the detergent, wt. parts:
Linear alkylbenzenesulfonate 25
CEMULSOL DB 618 ^® 3
CEMULSOL LA 90 ^® 2
(surfactant company SFOS)
Zeolite 4A 18
The product from example 14 25.8
SOKALAN CP5 ^® 4
(copolymer from BASF)
Carboxymethyl cellulose 1.5
TINOPAL DMSX 0.2
TIMOPAL SOP 0.2
(bleach company CIBA-GEIGY)
- ESPERASE ^® 0.3
(NOVO enzyme)
RHODORSIL 20444 ^® 2
(antifoam company RHONE-POULENC)
Sodium perborate, 4H ₂ O 15
TAED 3
pH (10 g / l) 10.25.

The test for removal efficiency is carried out in a washing machine FOM 71 ^® company WASCATOR.

The research conditions are as follows:
applicable cycle 60 ^o C,
total cycle time 70 min, without prewash;
number of cycles 3 per wash;
water hardness 32 ^o on the French scale;
load of linen 3.5 kg of white cotton rags;
during washing, the test fabrics are introduced by fastening them with pins and rags, two series of the following fabrics:
Gray cotton:
TEST-FABRIC
KREFELD 10C
IEC 106
EMPA 101
Polyester / Gray Cotton:
TEST-FABRIC
KREFELD 20C
EMPA 104
Protein stains:
Blood (EMPA 111)
Cocoa (EMPA 112)
Mixture (EMPA 116)
Oxidized spots:
Tea (KREFELD 10 C)
Raw Cotton (EMPA 222)
Wine (EMRA 114)
Dosage of detergent:
Series 1: 5 g / l, i.e. 5x20 100 g per wash;
Series 2: 8 g / l, i.e. 8x20 160 g for washing.

 Method for determining the removal of dirt and stains.

 Photometric measurements (measuring the amount of light reflected by the fabric) allow you to calculate the percentage of removal of contaminants. Use the ELREPHO 2000 device of DATACALOR firm.

где А отражающая способность образца-контроля белого цвета;
В отражающая способность загрязненного образца-контроля;
С отражающая способность загрязненного образца после стирки.Pollution removal is expressed by the formula:

where A is the reflectance of the sample control white;
The reflectivity of the contaminated sample-control;
With reflectivity of the contaminated sample after washing.

 Reflectivity is determined using the blue trichromatic component without the action of optical brighteners.

The number of measurements per sample 4
The number of samples for washing 2
Number of washes 3
Consequently, 4x2x3 24 measurements in relation to contaminants per product and concentration are studied.

The anti-scale test in the washing machine is carried out in a SCHULTESS SUPER 6 DE LUXE ^® drum machine.

The research conditions are as follows:
applicable cycle 60 ^o C;
total cycle time 65 min, without prewash;
number of cycles 25 full washings;
water hardness 21.2 ^o on the French scale;
fabric used for testing: strip as witness, exactly meeting the specifications developed by NFT 73.600;
loading of linen: 3 kg of terry towels made of cotton 100%
detergent dose: 5 g / l.

Dried samples subjected to 25 washes, weighed and calcined them at 900 ^o C.

 Determine the weight of the ash relative to the weight of the original samples.

 The results of various tests are given in table. 4.

Example 15. Prepare a detergent similar to example 14, replacing the modifying additive in the form of a mixture: zeolite 4A + product from example 14 + SOKALAN CP 5 with a modifying additive in the form of the following mixture, parts:
Zeolite 4A 30
Finely ground silicate R ₂ 3
Light carbonate 6
Sodium Sulfate 4.8
SOKALAN CP5 4
The results of tests to remove contaminants and against the formation of scale are given in table. 4.

Examples 16-18. The product from example 8 is introduced by mixing with the additives in the LODIGE M5G ^® device to obtain dishwasher compositions.

 Compositions are given in table. 5.

These compositions are tested in a MIELE ^® home dishwasher in which the water softener is not regenerated; therefore, it releases lime water having a total hardness of 30 ^° on a French scale.

 With each composition used with a concentration of 3 g / l of water, 10 full washes of calcium-sodium glass plates are carried out, completely clean at the initial moment.

 Then the plates are subjected to photometric measurement using a GARDNER identical to that used in examples 1 to 5.

 The total amount of light L reflected by the sample is measured.

 When the value of L is between 4 and 7, this result is considered very good: the glass is transparent.

 When the value of L is between 7 and 14, a light veil is visible.

The product from example 8 is compared, being in a composition quite close to the mixture of joint granules of sodium carbonate and of joint granules BRITSIL H ₂ O ^® (with a ratio of SiO ₂ / Na ₂ O 2 and containing 20% water, which is sold by PHILADELPHIA QUARTZ).

 The results are shown in table. 5.

 It was found that the use of joint granules from example 8 can reduce the amount of sodium citrate (expensive) and polyacrylate (biodegradable).

Comparative tests
1. Test A (invention)
Granulation is carried out according to the conditions of Example 10 and granules are obtained having the following characteristics,
Carbonate 54.5
Silicate 29
Water (total) 16.5
Silicate Water 16
i.e. ratio: water associated with silicate / dry silicate: 29/16 = 100/55.

At the inlet of the drum, the temperature of the drying air is 70 ^o C. At the outlet of the product, the temperature is 65 ^o C.

2. Test B (not corresponding to the invention)
Granulation was carried out as in test A, but the temperature at the inlet of the drying drum was 140 ^o C, at the outlet the temperature was 105 ^o C.

The obtained granules had the following characteristics,
Carbonate 55.5
Silicate 29
Water (total) 15.5
Silicate Water 4.5
i.e. the ratio: water associated with silicate / dry silicate 29 / 4,5 100 / 15,5.

The granules obtained in test A and in test B are introduced into a detergent composition of the following composition,
Sodium alkylbenzenesulfonate 6
Ethoxylated Alcohol 12
Pellets 35
Sodium Citrate 5
Acrylic Maleic Copolymer 5
Sodium Perborate 15
Tetraacetylethylenediamine 5
Phosphonate 0.3
Enzymes + methyl cellulose + antifoam silicone + sodium sulfate + bleach 16.7
Tests and methods for measuring the removal of contaminants were carried out according to example 14.

 The following results are obtained.

Washing rate
Pellets A 55.9
Co-granules B 54.8
Scale formation 5 g / l
Pellets A 1.8
Pellets B 3.1n

Claims (18)

1. Modifying additive in the form of particles for a detergent composition based on a carrier and an alkali metal silicate, characterized in that it contains the product of the absorption of an aqueous solution of alkali metal silicate having a dry extract of 10 60% with a molar ratio of SiO ₂ M ₂ O equal to 1, 6 3.5, M alkali metal, on an inorganic granular support chemically inert with respect to silicate, other than alkali metal tripolyphosphate, in the ratio based on dry weight, wt. Media 55 95
Alkali metal silicate aqueous solution Up to 100
and the mass ratio of silicate, calculated on its dry weight to water associated with it, equal to 100 120 100 40.  2. The additive according to claim 1, characterized in that it contains sodium carbonate as a carrier. 3. A method of obtaining a modifying additive for a detergent composition in the form of particles on the basis of a carrier and an aqueous solution of alkali metal silicate, comprising the absorption of alkali metal silicate on a carrier, characterized in that the absorption is carried out by spraying at 20 95 ^o With a concentrated aqueous solution of alkali metal silicate with a molar ratio of SiO ₂ M ₂ O equal to 1.6 3.5, and having a dry extract of 10 60% on an inorganic chemically inert silicate carrier other than sodium tripolyphosphate, the carrier being injected in such an amount that the amount of residual water with silicate after absorption corresponds to the mass ratio of silicate, calculated on its dry weight to water associated with silicate, equal to 100 120 100 40.  4. The method according to claim 3, characterized in that sodium carbonate is used as a carrier. 5. A method of obtaining a modifying additive for a detergent composition in the form of spherical co-granules of alkali metal hydrate silicates and alkali metal carbonate, comprising mixing alkali metal silicate and alkali metal carbonate, characterized in that the mixture is carried out by spraying at 20 95 ^o With an aqueous solution of alkali metal silicate with a molar ratio of SiO ₂ M ₂ O equal to 1.6 3.5, and having a dry extract of 30 55% or a mixture thereof with an alkali metal carbonate on a moving layer of particles based on an alkali metal carbonate p ri 15 200 ^o With an average range of particles of 10 150 microns, with a water content of 0.05 to 0.4 wt. and a filling density of 0.4 1.1 g / cm ² without tamping, wherein the particle passage speed, the thickness of the moving layer and the flow rate of the sprayable solution are controlled so that each particle turns into a plastic co-granule upon contact with other particles, then the obtained co-granules are compacted, dried to a water content associated with silicate corresponding to the mass ratio of silicate calculated on the dry weight to water associated with silicate equal to 100 120 100 40.  6. The method according to claim 5, characterized in that the particles of the moving layer contain less than 10% by weight of the co-granules of a particle of a different nature, different from alkali metal carbonate, and having a diameter and density close to the diameter and density of alkali metal carbonate particles.  7. The method according to claim 5, characterized in that the granulation is carried out in a rotating granulator, which ensures the passage of particles in thin layers.  8. The method according to claim 5, characterized in that a scraper conveyor is used as a rotating granulator.  9. The method according to claim 5, characterized in that the granulation is carried out in a granulation drum. 10. The method according to claim 5, characterized in that the moving layer of particles of alkali metal carbonate passes at 15 200 ^o C.  11. The method according to claim 5, characterized in that the amount of sprayable silicate solution or its mixture with carbonate and the number of particles of the carbonate carrier corresponds to a ratio of liquid flow to particle flow equal to 0.2 0.8 l / kg based on sodium salt.  12. The method according to claim 5, characterized in that the compaction of the granules is carried out at ambient temperature by rolling the co-granules obtained by granulation.  13. The method according to p. 12, characterized in that the seal is carried out in a rotating drum.  14. The method according to claim 5, characterized in that the drying of the granules after compaction is carried out in a fluidized bed.  15. The method according to claim 5, characterized in that after drying, liquid additives used in detergent compositions are added to the co-granules by spraying. 16. Spherical co-granules based on alkali metal hydrate-silicate absorbed on an alkali metal carbonate carrier obtained by the method according to claims. 5 to 15, characterized in that they contain alkali metal silicate with a molar ratio of SiO ₂ M ₂ O equal to 1.6 to 3.5 in the following ratio of components, wt. Alkali metal silicate 8 38
Alkali carbonate 47 87
Water 5 25
when the filling density without tamping is 0.7 1.5 g / cm ³ , the average diameter is 0.4 1.8 mm with a deviation of the order of log 10 from 0.02 0.3 and the mass ratio of silicate based on dry weight to residual water, associated with silicate, equal to from 100 120 to 100 40. 17. Spherical co-granules of alkali metal hydrate-silicate and sodium carbonate according to claim 16, characterized in that they contain alkali metal silicate with a molar ratio of SiO ₂ M ₂ O equal to 1.8 to 2.6, in the following ratio, wt. Alkali metal silicate 24 31
Sodium carbonate 64 69
Water 12 20
at a filling density without ramming of 0.7 1.5 g / cm ³ , preferably 0.8 1.0, an average diameter of 0.4 0.8 mm with a deviation of the order of log 10 from 0.05 to 0.1, the dissolution rate in water 90% for a time of less than 2 minutes and 95% for a time of less than 4 minutes, and the mass ratio of silicate to dry weight to residual water associated with silicate is from 100 120 100 40.  18. Detergent powder composition for dishwashers and washing machines, including surface-active substances, a modifying additive and organic and inorganic additives, characterized in that it contains as a modifying additive coranules according to claims 16 to 17 in the following ratio of components, wt. Surfactants 8 20
Modifying additive 3 90
Organic and Inorganic Additives Up to 100
19. The composition according to p. 18, characterized in that it contains a modifying additive in an amount of 3 to 60% by weight of the composition based on dry silicate.

Images