SK191992A3 - Builder agent into detergent mixtures and method of its preparing - 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 builder consisting of alkali metal silicates rich in the types in which the silicon atoms are in the form α and β, and useful for detergent compositions, in particular powder detergent compositions, for washing machines and dishwashing machines.

-¾

BACKGROUND OF THE INVENTION

By builder is meant any active ingredient that improves the performance of surfactants in detergent compositions.

It is essential that the builder have a so-called softening effect on the water used for washing or washing. It must therefore remove calcium and magnesium present in water in the form of soluble salts and in the dirt of the laundry in a complex, more or less soluble form. Removal of calcium and magnesium can be accomplished either by complexing them, by ion exchange or by precipitation. In the event of precipitation, this process should be controlled to prevent the formation of precipitates formed on the laundry or inside components of washing machines or dishwashers.

In particular, such controlled precipitation is achieved by the use of water-soluble polymers having affinity for calcium and magnesium.

The builder also needs to promote the emulsifying effect of the surfactants towards the greasy dirt and the dispersing effect towards the pigment dirt, which is mainly formed by metal oxides, clay, silica, various powders, humus, limestone and soot.

This dispersing effect is generally achieved by

- 2 the presence of polyanions which impart a high negative charge density to the interfaces.

It is also necessary that the builder provide an ionic strength favorable to the function of the surfactants, in particular by increasing the micelle size.

In addition, the builder needs to supply OH ions for saponification of the fat as well as for increasing the surface negative charges on the fabric surface and on the particulate dirt.

Silicates have long been considered good detergent ingredients, although less currently used in compositions for phosphate-free washing machines.

The most widely used silicates are silicates having a SiO ₂ / Na ₂ O molar ratio ranging from 1.6 to 2.4. These silicates are commercially available either in the form of concentrated solutions having a dry matter content of 35 to 45% by weight or in the form of a silicate, optionally compressed powder.

Concentrated commercial solutions are most commonly prepared from a completely amorphous silicate, known as glassy silicate, which is a form of amorphous silicate. is also known as water glass.

These waterglasses are dissolved in water in an autoclave under pressure at 140 ° C. In this way, commercial solutions are obtained having a dry matter content of about 45% by weight for the silicate ratio 2 and about 35% by weight for the silicate ratio 3.5.

These concentrated silicate solutions are then formulated by the detergent formulation manufacturer into an aqueous suspension (slurry) containing the other detergent ingredients. The resulting slurry is then dried in a spray drier. The silicate which is thus sprayed together and dried together with the other components then contains not more than 20% of the associated water, based on its dry weight, or contains less water.

As regards the commercial silicate powder, this powder is obtained by drying in a spray-drying glassy silicate; 20 to 22% by weight of water in the final product must be maintained to ensure good solubility of the product.

It has now been found that when the silicate is dissolved in the wash liquor in an amount of 1 to 3 g / l, the silicate powder, which contains only 20 to 22% by weight of the accompanying water (based on the mountain product), weak builder properties.

In fact, this dissolved silicate powder provides monomeric silicon-containing compounds of the general formula f Si (OX) ₄ in which X is a hydrogen atom or a sodium atom which does not have a builder effect. Such monomeric silicon-containing substances are able to associate with each other and thus form polyanions only when the silicate concentration is at least 50 to 500 g / l, and even then the process is very slow.

Such silicate concentrations and such slow polymerization kinetics of the monomer substances are incompatible with the washing conditions and washing time.

What has been found for a powder containing 20 to 22% chemically bound water (based on the finished product) also goes without saying also for formulations containing a silicate with 20% accompanying water (based on the dry weight of silicate) and prepared by introducing a concentrated silicate solution into suspension and co-drying.

It has now been found that if an alkali metal silicate is rich in the silicate types in which the silicon atoms are in the form of a Q 2, then the polyanionic substances formed by diluting to a concentration of 1 to 3 g / l in the detergent medium have sufficient durability to play the role of a detergency builder.

The term silicon atoms has the form and Q 1 reflects the degree of mutual association of silicon atoms; form Q2 means the form in which each silicon atom participates in two bonds -Si-O-Si-, the remaining two bonds being

- 4 bond bonds -Si-OX, wherein X represents an alkali metal or hydrogen atom, while form Q ^ means that each silicon atom participates in three bonds -Si-O-Si-, the remaining bond being the terminal bond -Si- OX wherein X is as defined above.

SUMMARY The agents of the builder for the detergent composition of the invention is that it is made up of an alkali metal silicate, particularly sodium or potassium silicate, containing at least 30% and preferably at least 50% of the silicon atoms in the form of Q ₂ and Q ^.

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

Said builder agent may be in any form and may or may not have a structure (powder, granules and the like).

A first embodiment of the invention comprises a builder agent comprising an aqueous solution comprising about 10 to 60%, preferably about 35 to 50%, by weight of the dry matter of an alkali metal silicate, especially sodium or potassium silicate, having a SiO ₂ / M ₂ O molar ratio of about 1.6 to 3.5, preferably about 1.8 to 2.6.

The concentrated alkali metal silicate solution used as builder reagent is preferably obtained by dissolving in aqueous waterglasses in an autoclave under pressure at 140 ° C and optionally subsequent dilution; this concentrated solution may also be obtained by other known methods, for example by directly treating the concentrated sodium hydroxide solution on the sand.

Nuclear magnetic resonance spectroscopic analysis found that:

- a solution with 45% dry silica glass having a SiO ₂ / Na ₂ O molar ratio of 2 contains 34% of the form, 51% of the form Q ₂ , 12% of the form Q ₁ and 3% of the form Q _Q, and

- a solution with 35% dry silica glass having a SiO ₂ / Na ₂ O molar ratio of 3.5 contains 46% of form Q 4,% of form 16% of form Q ₄ , 9% of form Q ₁ and 2% of form Οθ.

The solution can thus be added (post addition) to the detergent by spraying it onto the detergent powder at the bottom of the tower in the case of a spray device or by spraying it into a mixture of detergent formulation components in a dry mixture. The powder mixture thus obtained may then optionally be slightly dried so that the weight ratio of dry silicate / residual water bound with silicate is in the range of 100/120 to 100/40, preferably in the range of 100/90 to 100/50.

The silicate solution may be used in an amount such that the dry silicate / detergent powder weight ratio is in the range of 1/100 to 30/100, preferably in the range of about 10/100 to about 20/100.

Another non-limiting embodiment of the invention comprises an aqueous solution containing about 10 to 60% by weight, preferably about 35 to 50% by weight, of the dry matter of alkali metal silicate, especially sodium silicate or potassium silicate, having a SiCl2 / H2O molar ratio of about 1.6 to 3 5, preferably about 1.8 to 2.6, absorbed in a particulate carrier which is inert to the silicate and / or adsorbed on such carrier, wherein the weight ratio of silicate dry matter / residual water bound to the silicate is in the range of from 100/120 to 100/40, preferably in the range from 100/90 to 100/50.

The term inert means chemically inert.

The term silicate-bound water refers to water in a solution carried on a carrier which has not been combined with an inorganic carrier, in particular in the form of a crystalline hydrate.

Examples of inorganic carriers for a silicate solution are those which are preferably water-soluble, such as: sodium carbonate, sodium sulfate, sodium borate, sodium perborate, sodium metasilicate and phosphates or polyphosphates such as sodium phosphate and sodium tripolyphosphate, wherein the carriers are present alone or in admixture with each other.

The carrier generally represents about 55 to 95%, preferably 65 to 85% by weight of the supported solution in the dry state (i.e. dry weight of solution + carrier weight).

Said supported solution may be prepared by adsorption and / or absorption in which a concentrated aqueous alkali metal silicate solution having a SiO ₂ / M ₂ O molar ratio of about 1.6 to 3.5, preferably about 1.8 to 2, is used. 6, having a dry matter content of about 10 to 60%, preferably about 35 to 50%, contacted with an inorganic carrier which is inert to the silicate, said carrier being present in an amount such that the amount of residual water bound to said silicate after adsorption; and / or the absorption corresponds to a silicate / water dry weight ratio of silicate bound to about 100/120 to 100/40, preferably about 100/90 to 100/50.

Said contacting of the concentrated aqueous silicate solution with an inorganic inert carrier may be accomplished by adding, for example, spraying said concentrated silicate solution to the carrier in particulate form in any known high shear mixer, in particular in a Lodige mixer or granulating mixer. apparatus (drum, plate, and the like) at a temperature of about 20 to 95 ° C, preferably about 70 to 95 ° C.

Applicable carriers have already been mentioned above.

The amount used and the concentration of the silicate solution used depend on the absorption and / or adsorption capacity of the carrier, taking into account the possibility that said carrier may in particular be crystallizable hydrates; the aqueous fraction which is not bound with the silicate and which may be part of the hydrate form in the carrier can be determined in a known manner using differential thermal analysis or quantitative X-ray diffraction analysis. Any other fraction of water that is bound to the carrier in a non-hydrate form can be determined by a suitable physical chemical method (thermoporosimetry, thermogravimetric analysis, proton nuclear magnetic resonance spectroscopy, infrared spectroscopy).

The limits of the adsorption and / or absorption capacity of said carrier can be determined by known methods, for example by measuring the change in slope angle of the test carrier pile depending on the amount of silicate solution added.

If desired, the carrier / silicate solution mixture may be dried, but moderate to the extent that the silicate bound water is attained.

The resultant particles of supported silicate solution can then optionally be milled to obtain a mean particle diameter of about 200 to 800 microns.

Particularly powerful builder agents of the invention are alkali metal silicate solutions in absorbed and / or adsorbed form on the alkali metal carbonate, which are in the form of spherical mixed granules of hydrated alkali metal silicate and alkali metal carbonate.

Said spherical mixed granules of hydrated alkali metal silicate and alkali metal carbonate may be prepared by a process comprising:

- an aqueous solution of alkali metal silicate or of a mixture of alkali metal silicate and alkali metal carbonate is sprayed onto the rolling bed of the alkali metal carbonate particles moving in a rotary granulation device, the particle velocity, rolling bed thickness and flow rate of the spray solution being selected such that each particle is converted into a plastic blend granule after contact with the other particles, and then is formed

the mixed granules thus obtained are subjected to a compacting operation, and

- the compacted blended granules obtained are dried to obtain a silicate-bound water content corresponding to a silicate / water dry weight ratio of silicate-bound equal to about 100/120 to 100/40.

Preferred examples of alkali metal silicate and alkali metal carbonate are sodium silicate and sodium carbonate and potassium silicate and potassium carbonate, with sodium silicate and sodium carbonate being particularly preferred.

The sprayed aqueous solution based on a silicate or a mixture of silicate and carbonate may have a dry matter content of about 30 to 55% by weight, preferably 30 to 45% by weight; said alkali metal silicate has a SiCl 2 / I 2 O molar ratio of about 1.6 to 3.5, preferably about 1.8 to 2.6, and particularly close to 2; said carbonate may optionally be present in an amount depending on the desired end product.

Injection of the silicate or silicate-carbonate solution is carried out at a temperature of 20 to 95 ° C, preferably at a temperature of about 70 to 95 ° C; the spraying may be aided by the simultaneous introduction (for example using a nozzle for discharging two fluids) of compressed air of the same temperature.

The particles used for preparing the mixed granules are predominantly alkali metal carbonate having:

- a mean diameter of about 10 to 150 microns, preferably about 20 to 100 microns, and particularly close to 30 to 80 microns,

- non-bulk density

2 about 0.4 to 1.1 g / cm, preferably about 0.6 to 1.1 g / cm,

a water content of about 0.05 to 0.4%, preferably 0.1 to 0.3%, by weight and

an amount of insoluble matter of about 5 to 100 mg / kg, generally about 10 to 60 mg / kg.

Conventional ground or unground carbonate may be used in this regard.

In addition to these carbonate particles, they can be used

- 9 small amounts (less than 10% by weight based on the total weight of the mixed granules) of other particles, such as, in particular, antiredepozoic polymers (carboxymethylcellulose and the like) and enzymes which are commonly used in the detergent sector; density close to diameter and density of carbonate particles.

The apparatus used to carry out the mixed granulation process by spraying may be any rotary plate rotating device, a rotating disc or a rotating drum, or a mixer-granulator type device or the like.

A first preferred method of making these mixed granules is to use a rotary granulator to allow the particles to move in the form of a thin film.

Particularly suitable for this purpose are discs having an angle greater than 20 [deg.], The axis of rotation inclined to the horizontal preferably being greater than 40 [deg.]; their geometry can be very diverse, for example having a flat or stepped shape or a truncated cone shape.

A second preferred method of making these mixed granules is to use a rotary drum having an inclination angle of at least 3% and preferably at least 5%.

The carbonate-based particles in the granulation apparatus are at a temperature of about 15 to 200 ° C, preferably at a temperature of about 15 to 200 ° C, and especially at a temperature of 15 to 30 ° C.

The amount of the silicate-based or silicate-carbonate-based solution to be sprayed onto the carbonate-based particles corresponds to a liquid flow / particle flow ratio which may be 0.2 to 0.8 l / kg, preferably 0.4 to 0 7 l / kg and in particular 0.62 to 0.7 l / kg, these values refer to sodium salts.

The flow rate of the spray solution, the rate at which the particles move, and the thickness of the moving particle layer are selected such that each particle absorbs a portion of the spray solution and agglomerates with the other particles it comes into contact to obtain plastic granules and not paste.

The rate at which the particles move within the granulation apparatus and the thickness of their layer are controlled by the amount of particles introduced into the granulation apparatus per unit of time and by the characteristics of the granulation apparatus itself.

The residence time of said particles in a plate or drum type granulator generally ranges from about 15 to about 40 minutes.

For the skilled artisan, it will be a routine matter to modify the characteristics of the granulation apparatus to obtain the desired product from a given starting product, which in the case of a plate (disk) can be achieved by selecting:

- its geometry (plate in the form of a truncated cone, a flat cone, a stepped cone or in the form of a combination of the three shapes),

- its size (depth, diameter),

- its angle of inclination,

its rotation speed, and

the relative position of the solids inlet and the feed solution inlet;

whereas in the case of a drum this can be achieved by choosing:

- its geometry (diameter),

- its angle of inclination,

- its rotation speed,

its contents, and

- the relative position of the solids inlet and the feed solution.

The thus obtained non-compacted and non-dried mixed granules

1 have properties which depend on the conditions used in the granulation process. These mixed granules have:

- a silicate content of about 7 to 30% by weight, preferably about 11 to 23% by weight, and in particular about 21 to 23% by weight,

- a carbonate content of about 41 to 75% by weight, preferably about 48 to 64% by weight, and in particular about 48 to 51% by weight, and

a water content of about 18 to 29% by weight, preferably 25 to 29% by weight, and in particular about 27 to 29% by weight.

The compaction process can be carried out at ambient temperature by rolling the mixed granules obtained in the granulation step in a rotary device.

The rotary device is preferably independent of the granulation device.

Said compacting step may advantageously be carried out by introducing said mixed granules into a rotary drum and leaving said particles in said drum for a period of time. The inclination angle of the rotary drum is at least 3%, preferably at least 5%. The dimensions of the drum, its rotation speed and the residence time of the mixed granules therein will depend on the desired density of the mixed granules; the residence time of the mixed particles in the drum is generally about 20 minutes to 3 hours, preferably about 20 to 90 minutes.

Mixer-granulators may also be suitable for this compacting operation.

The blend granulation and densification can also be carried out in one device, for example on a stepped disc, wherein the compaction of the blend granules is achieved by rolling said blend granules at the final stages of the disc; alternatively, the two operations may be performed in a dual-zone drum.

2

The compacted mixed granules are then dried by known means. A particularly efficient method of drying the compacted mixed granules is to dry them in a fluidized bed formed by an air stream having a temperature of about 40 to 90 ° C, preferably 60 to 80 ° C. The duration of the drying operation is dependent on the temperature of the air used to form the fluidized bed, the water content of the mixed granules at the outlet of the granulation apparatus and the water content to be dried of the mixed granules, as well as the fluidization conditions; one of ordinary skill in the art will routinely set these different conditions to obtain the product of the desired parameters.

Dried compacted mixed granules in general have:

- a silicate content of 8 to 38% by weight, preferably 14 to 31% by weight and in particular 24 to 31% by weight,

- a carbonate content of about 47 to 87% by weight, preferably about 59 to 81% by weight and in particular about 64 to 69% by weight,

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

a bulk density of the unshaked filling of about 0.7 to 1.5 _w 3 g / cm, preferably about 0.75 to 1.5 g / cm, and in particular about

0.8 to 1 g / cm a

- a mean diameter (relative to the cumulative sink) of about 0.4 to 1.8 mm, preferably about 0.6 to 0.8 mm, with a log standardní standard deviation of 0.02 to 0.3, preferably 0.05 to 0, 1.

Said mixed granulation, compacting and drying stage makes it possible to obtain mixed granules which are based on hydrated alkali metal silicates and alkali metal carbonates which are perfectly spherical and dense and which dissolve rapidly in water.

Hydrated sodium silicate-based and sodium carbonate-based spherical granules which are particularly suitable for the preparation of detergent compositions for dishwashers and washing machines are mixed granules having:

3

- a silicate content of about 24 to 31% by weight,

- a carbonate content of about 64 to 69% by weight,

- a water content of 12 to 20% by weight,

a specific weight of the unstretched filling of about 0.7 to 1.5 g / cm @ 2, preferably about 0.8 to 1,

- average diameter of about 0.4 to 0.8 of a log-θ ₁ standard deviation of 0.05 and 0.1, and

a 90% dissolution rate of less than 2 minutes and a 95% dissolution rate of less than 4 minutes.

The term 90% or 95% dissolution means the dissolution of 90% or 95% of the product in water and a rate of 90% or 95% dissolution therefore means the time necessary to dissolve 90% or 95% of the product to a concentration of 35 g / l in warm water. Deň: 18 ° C.

The builder agent of the invention having a structure (powder, blend granules and the like) is used in a dishwashing detergent composition in an amount of 3 to 90% by weight, preferably in an amount of 3 to 70% by weight, based on the weight of said compositions; the amount of the builder reagent used in the washing machines is about 3 to 60% by weight, preferably 3 to 40% by weight, based on the weight of said compositions (these amounts are expressed as dry weight of silicate relative to the weight of the composition).

In addition to the builder agent of the present invention, the detergent composition comprises at least one surfactant in an amount which may range from 8 to 20% by weight, preferably from about 10 to 15% by weight, based on the weight of said composition.

The following surfactants include:

- anionic surfactants of the type comprising alkali metal soaps (alkali metal salts of fatty acids with 8 to 24 carbon atoms in the chain), alkali metal sulfonates (alkylbenzenesulfonates with up to 13 carbon atoms in the chain and alkylsulfonates with 12 to 16 carbon atoms, in ethoxy)

4-C 6 and C 16 fatty alcohols, oxyethylene and sulphated C 8 -C 13 alkylphenols, alkali metal sulfosuccinates (C 12 -C 16 alkylsulfosuccinates) and the like,

- non-ionic surfactants of the type comprising 6 to 12 carbon atoms of polyoxyethylenated alkylphenols, oxyethylenated aliphatic alkylphenols of up to 22 carbon atoms, ethylene oxide-propylene oxide block copolymers and optional polyoxyethylenated carboxylic acids,

amphoteric alkyldimethyl betaine - type surfactants; and

cationic surfactants of the type comprising alkyltrimethylammonium chlorides or bromides and alkyldimethylethylammonium chlorides and bromides.

Various other ingredients may also be included in the detergent composition, such as:

- builders of a type comprising:

- phosphates in an amount of at least 25% by weight, based on the total weight of the formulation,

-zeolites in an amount of up to about 40% by weight of the formulation,

- sodium carbonate in an amount of up to about 80% by weight of the formulation,

nitriloacetic acid in an amount of up to about 10% by weight of the formulation and

- citric acid or tartaric acid in an amount up to about 20% by weight of the formulation, the total amount of builder corresponding to about 0.2 to 80% by weight, preferably 20 to 45% by weight, based on the total weight of said detergent composition,

5

- bleaching agents of the type comprising perborates, percarbonates, chloroisocyanurates and N, N, N ', N' -tetraacetylethylenediamine (TAED) in an amount of up to 30% by weight, based on the total weight of said detergent composition,

- anti-redeposition agents of the type comprising carboxymethylcellulose or methylcellulose in an amount which may be up to about 5% by weight, based on the total weight of said detergent composition,

- anti-incrustants of the type comprising acrylic acid and maleic anhydride in the form of copolymers in an amount which may amount to up to about 10% by weight, based on the total weight of the detergent composition, and

sodium sulphate fillers for powdered detergents in an amount which may be up to 50% by weight, based on the total weight of said detergent composition.

In the following, the invention will be further elucidated by means of specific exemplary embodiments thereof, which are illustrative only and are not intended to limit the scope of the invention as defined by the claims.

DETAILED DESCRIPTION OF THE INVENTION

Examples 1 to 5

Builder performance characteristics

- a sodium silicate solution with a molar ratio SiC> 2 / Na 2 O = 2 and a dry matter content of 45% by weight (Example 2), and

- sodium silicate solution with a SiO ₂ / Na ₂ O molar ratio of 3,4 and a dry matter content of 35% by weight (Example 4)

6 is determined in a tergotometer (US Testing Company, Hoboken, USA) in a binary mixture with an anionic surfactant LABS (linear sodium dodecylbenzene sulfonate commercially available from Aldrich) using reflectance measurements using a Gardner reflectometer.

These performance characteristics are compared to the performance characteristics:

- the anionic surfactant LABS alone at a concentration of 2 g / l (Example 1),

- a sprayed silicate powder with a ratio of 2 to% water (i.e. 28.2% water based on the silicate dry matter) (Example 3), and

- a sprayed silicate powder having a ratio of 3.4 and 18.6% water (i.e. 22.8% water based on the silicate dry matter) (Example 5) used under the same conditions (4 g / l).

The results of these determinations are shown in Table I below.

Measurement method

principle

Simplified laundry washing is simulated in a tergotometer in which soiled fabric samples are washed at 65 ° C using a surfactant and a builder to be tested. Washing lasts 20 minutes, the fabric color being determined before and after washing. Simultaneously, a blank test is carried out in which the same type of fabric is washed using only a surfactant, and then the performance of the builder tested is evaluated by comparison with the results of the blank. Test methodology

The tergometer is a device consisting of 4 2 liter containers holding pulsators that are set

7 per 100 cycles per minute. Said containers are placed in a tank of water which is thermostatized to 65 ° C.

1) Pour 1 liter of hard tap water (34 ° French total hardness) into each container;

when the water is at the desired temperature, the containers are placed:

5 white cotton samples of 405 W pattern available from Test Fabric; the sample size is 10 x 12 cm;

5 samples of white polyester cotton (PEC) type 7435 commercially available from Test Fabric; sample size x 12 cm;

- 2 cotton samples contaminated with EMPA (ink and olive oil) commercially available from Gallen under the designation 101; the sample size is 10 x 12 cm;

- 2 cotton samples contaminated with red wine (114 from Gallen); the sample size is 10 x 12 cm;

- 2 samples of polyester cotton (PEC) contaminated with EMPA (104 from Gallen); sample size is 10 x 12 cm ·.

(2) The following three operations shall be carried out simultaneously:

- the stopwatch starts,

mixing is involved, and

a mixture of builder and surfactant is added.

The builder is tested at a concentration of 4 g / l (expressed as the dry matter of the material in the product) and the surfactant LABS is added.

3) Rinse

After 20 minutes, the wash water is drained and the fabric is rinsed with 3 x 1 liter cold tap water.

4) Centrifugation and drying

8

The rinsed fabric samples are centrifuged and pre-dried by spreading the individual fabric samples onto the suction paper. The textile is then passed twice between two rollers provided with suction paper at a temperature of about 110 ° C.

5) Determination of color

In Gardner, zero is measured by measuring the black plate intended for this purpose, then the L, a and b values are read using a standard white plate of the same type as the black plate.

L sets the color in shades from white to black.

L = 100 corresponds to the white sample

L = 0 corresponds to the black sample;

and situates the color in shades from green to red.

and is greater than zero: the color is approaching red and is less than zero: the color is approaching green;

b sets the color in shades from yellow to blue.

b is greater than zero: the color is close to yellow b is less than zero: the color is close to blue.

After the calibration, the determination is made. Two samples of each textile category are removed from each container and 5 determinations per sample (one in the middle of the sample and one in each corner of the sample) are carried out, placing a heavy metal plate on the fabric. The arithmetic mean is then calculated from ten determinations. The same procedure applies to un washed laundry.

6) Calculation of the result

DL and DE values are calculated for each test and for each textile type.

DL = L after washing - L before washing

Da = a before and after washing

9

Db = b before washing - b after washing

DE = V DL ² + Da + Db ^{2 2} = detergency.

The mean DL and DE shall be calculated for each product and for each type of soiled fabric. Then, for each product, calculate:

Det (ergence) EMPA cotton = medium DE EMPA cotton Det (ergence) EMPA PEC = medium DE EMPA OVEN Det (ergence) WINE cotton = medium DE WINE cotton

Det (ergence) cumulative = sum of detergents EMPA cotton, EMPA Furnace and WINE cotton.

Examples 6 and 7

800 g of anhydrous tripolyphosphate, commercially available from Rhône-É’oulenc, was introduced into a Lodige M5G blender (commercially available from Lodige).

After closing the apparatus and starting its rotation at 400 rpm, 200 g of a sodium silicate solution having a SiO2 / Na2O molar ratio of 2 and containing 45% by weight of dry matter are introduced by spraying.

This addition lasts 10 minutes; after a further 10 minutes of mixing by rotation, the product is discharged and left to stand for 2 hours at ambient temperature on the plate. The product thus obtained has the following characteristics:

- partial hydrated tripolyphosphate: 82% by weight,

- sodium silicate: 9% by weight,

- silicate bound water: 9% by weight, i. 100% based on silicate dry matter.

The total amount of water contained in the product is determined by measuring the weight loss of the product after heating to 500 ° C; on the contrary, the amount of water bound in the form of hydrates is determined by differential thermal analysis. The quantity of water bound with the silicate is calculated as the difference between the total water content and the water content bound in the form of hydrates.

- mean diameter = 250 micrometers.

The builder performance characteristics of this product were using the method described above except that 2 samples of PEC were contaminated with EMPA art. 104 will replace 2 cotton samples contaminated with WFK from Krefeld of the same size (Example 6).

These performance characteristics are compared to the performance characteristics of a mixture of anhydrous tripolyphosphate TPP and a sprayed silicate powder having a SiC> 2 / Na 2 O ratio of 2 and a moisture content of 22% in a TPP / silicate dry weight ratio of 800/90. (4 g / l) (Example 7).

The results of these determinations are shown in Table II below.

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Cumulative Det 58,96 57,66

Example 8

The granulation system used in this example comprises a flat plate having a diameter of 800 mm and a depth of 100 mm. During granulation, the plate is rotated at a speed of about 35 rpm and its axis of rotation is inclined to the horizontal by an angle of about 55 °. A powder consisting of fine particles of sodium carbonate having the following main characteristics is fed continuously to the granulation plate at a rate of 21.4 kg / h:

- alkalinity: 99,61%,

- water content (mass): 0,12%,

- density of unshelled filling: 0,56 g / cm ³ ,

mean particle diameter: 95 micrometers, and

- content of insoluble matter: 58 mg / kg.

A sodium silicate solution having a temperature of 80 ° C and injected at a rate of 13.4 l / h through a two-neck nozzle, the mouth of which is 20 cm from the bottom of the plate, is sprayed onto the powder using an 80 ° C hot air stream. The amount of active material (dry matter) is 43% and the SiO ₂ / Na ₂ O molar ratio is 2. The dry matter of the active material is expressed in weight percent.

The mean residence time of the particle in the granulation plate is about 10 to 15 minutes. The temperature of the particles leaving the plate is equal to the ambient temperature.

The granules leaving the granulating plate are then introduced into a rotating tube with smooth inner walls having a length of 1300 mm, a diameter of 500 mm and a slope of about 5%. The outlet baffle is adjusted so that the mean residence time of the granules in the tube is about 40 minutes. The rotation speed of the tube (18 rpm) is adjusted so as to obtain a rolling bed of particles which favorably affects the compaction of the particles.

The granules so obtained are dried in a fluidized bed at a temperature of about 80 ° C (fluidizing air temperature of about 85 to 90 ° C) for 10 to 15 minutes.

The product thus dried has the following characteristics:

- carbonate content (mass): 65%,

- silicate content (w / w): 21% + 0,5%,

- water content (mass): 13,5%,

- density of unshelled filling: 0,90 g / cm ³ ,

- Oversize 1% by weight: 10,8%,

- mean particle diameter: 0,73 mm,

- percentage drop by mass 0,2 mm: 6%,

- 90% (w / w) of the product dissolve within seconds (aqueous solution at 35 g / l at 20 ° C),

- 95% (m / m) of the product is dissolved in seconds (35 g / l aqueous solution at 20 ° C),

- whiteness L: 96,3,

- Abrasion resistance: 7%.

The granules obtained have excellent storage stability.

Determination of abrasion resistance

Technical equipment:

The standard equipment used to determine the quality of the hydraulic binders, as described in French standard P 15-443 and referred to as a flourometer, is used.

Methodology of determination:

Using a Roto-Lab laboratory sifter (commercially available from Prolabo), 50 g of product is sieved between sieves with a mesh size of 1200 and 180 microns. A product fraction with a particle size between 180 and 1200 microns is obtained.

Weigh accurately about 25 g of the test product; this exact mass will also be designated as M.

This weighed product is fed into a flourometer. A weighed Soxhlet type dry and dry filter (commercially available from Prolabo) is placed in the top of the fluidizing tube; its mass is equal to M1.

The fluidization process is then started and allowed to proceed for 5 minutes (dry air flow: 15 l / min).

Then, the product that has been entrained in the filter and the fine particles that may have adhered to the walls of the fluidization tube using a roller brush on a suitable diameter rod are isolated. This fine fraction is weighed together with the filter and the weight is indicated as M2.

The remainder of the bottom of the fluidizing tube is sieved again in a Roto-Lab sieve, and a sink of less than 180 microns is weighed. The weight of this sink is designated as M3.

Calculation. Expression of result:

The degree of abrasion corresponds to the percentage of fine particles less than 130 microns formed during the fluidization.

fM3 + M2)

Strap A% (%) = —-------------------- x 100.

M

Example 9

The procedure described in Example 1 was repeated, but was modified as follows:

granulation:

- granulating plate: rotation speed 30 rpm,

amount of powder introduced: 22 kg / h a

- amount of silicate solution introduced: 13 l / n.

compaction:

- drum rotation speed: 10 rpm.

Fluidized bed drying:

- temperature: 90 ° C,

- time: 20 minutes.

The dried product has the following characteristics:

- carbonate content (by weight): 60,9%,

- silicate content (mass): 22,9 + 0,5%,

- water content (mass): 16,1%,

- density of unshelled charge: 0,86 g / cnX,

- Oversize 1% by weight: 2,6%,

- mean particle diameter: 0,64 mm,

- 0,2% mass drop by mass: 7,3%,

- 90% (w / w) of the product dissolve within seconds (aqueous solution at 35 g / l at 20 ° C),

- 95% (m / m) of the product is dissolved within 102 seconds (a 35 g / l aqueous solution at 20 ° C),

- whiteness L: 95,6 a

- Abrasion resistance: 9.2%.

These granules have excellent storage stability.

Example 10

In this example, a granulation system is used comprising a smooth inner wall drum having a diameter of 500 mm, a length of 1300 mm and a rotating speed of 40 rpm. The angle of inclination of the drum is 7.5%. The outlet baffle is set so that the mean residence time of the particle in the drum is about 15 to 20 minutes.

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

A silicate solution (containing 45.6% by weight of active material (dry matter) and having a SiO by weight ratio) is sprayed onto the powder, which rotates in the drum, using a flat two-necked nozzle located in the first third of the drum. ₂ / Na ₂ O equal to 2) having a temperature of 80 ° C and fed at 18 1 / h.

The mixed granules at the outlet of the drum have an ambient temperature and a density of 0.68 g / cm @ -1.

The blended granules are then compacted in a batch-like manner for one hour in a smooth-wall rotary drum having a diameter of 500 mm, a length of 1300 mm and a slope of 5%. The rotation speed of this drum is 20 rpm.

The granules so obtained are then dried in a fluidized bed at a temperature of about 65 ° C (fluidizing air temperature 70 ° C) for 15 minutes.

The product thus dried has the following characteristics:

- carbonate content (by weight): 62%,

- silicate content (by weight): 20,5% + 0,5%, - water content (by weight): 17,6%,

- density of unshelled charge: 0,820,

- Oversize 1% by weight: 5%,

- mean particle diameter: 0,65 mm,

- 0,2% weight loss by weight: 0,6%,

- 90% (w / w) of the product is dissolved in seconds (aqueous solution at a concentration of 35 g / l at 20 ° C),

- 95% (w / w) of the product is dissolved in seconds (35 g / l aqueous solution at 20 ° C).

These granules have excellent storage quality.

Example 1 1

The procedure described in Example 3 was repeated except that the procedure was modified as follows:

compaction:

- batch for 2 hours.

The dried product has the following characteristics:

- carbonate content (by weight): 60,8%,

- silicate content (mass): 19,3% + 0,5%,

- water content (mass): 19,9%,

- specific gravity of unshelled filling: 0,91 g / cm \

- Oversize 1% by weight: 1,6%,

- mean particle diameter: 0,57 mm,

- 0,2% mass drop by weight: 1,22%,

- 90% (w / w) of the product is dissolved in seconds (aqueous solution at 35 g / l at 20 ° C), and

- 95% (w / w) of the product is dissolved within 45 seconds (35 g / l aqueous solution at 20 ° C).

These granules have excellent storage stability.

Examples 12 and 13

The builder performance characteristics of the blended granules of Example 8 were determined as described in Examples 1 to 5.

These performance characteristics are compared to those of a mixture of sodium carbonate powder and atomized sodium silicate powder having a SiO2 / Na2O ratio of 2 and containing 22% in the final product (i.e., 28.2% water based on silicate dry weight) at a weight ratio of 3 / 1 (carbonate / atomized R2).

The results obtained are shown in Table III below.

The amounts of carbonate and silicate given in the table are expressed as dry matter.

It has been found that the performance characteristics of said blended granules are better than the performance characteristics of said blend of powders having the same silicate / carbonate ratio.

Example 14

Using the procedure of Examples 6 and 7, particles of:

1800 g of lightweight powdered sodium carbonate, having a mean diameter of about 110 micrometers, and

- 1200 g sodium silicate solution having a molar _SiO2 / Na ₂ O of 3.4 and a solids content of 37%.

After addition of the silicate solution for 5 minutes, mixing for 5 minutes and after standing for two hours in air at ambient temperature, a product is obtained having the following characteristics:

- carbonate content: 60% by weight,

- silicate content: 20% by weight,

silicate - bound water content: 20% by weight (ie.

100%, based on dry weight of silicate) and

- mean particle diameter: 4Ό0 micrometer.

This dry blended product is mixed with the ingredients to form the following laundry detergent composition:

The detergent composition component number (parts by weight) linear alkylbenzene sulfonate 25 Cemulsol DB 618 3 Cemulsol LA 90 2

3.0 (surfactants from S.F.O.S) zeol.it 4A18 product of Example 14

25.8

Sokalan CP54 (copolymer from BASF) carboxymethylcellulose 1.5

Tinopal DMSX 0.2

Timopal SOP0,2 (brighteners from fi

Ciba-GEICAM)

Esperase0,3 (enzyme from Novo)

Rhodors i 1 (anti-foaming agent from Rhône-Poulenc) sodium perborate in the form of tetrahydrate 15

TAED pH (10 g / L) = 10.25

The dirt removal performance test is performed in a Wascator FOM 71 washing machine.

The following conditions apply to the test:

- cycle used: 60 ° C,

- total cycle time: 70 minutes, without prewash,

- cycle number 3 / detergent,

- water hardness: 32 ° French water hardness,

- load: 3,5 kg white cotton rag

- test textiles: the following two series of textiles are introduced at each wash by pinning them to the rags:

gray cotton:

polyester / gray cotton:

protein dirt:

oxidizable dirt:

test textiles

Krefeld 10 C

IEC 106

EMPA 101 test textile

Krefeld 20 C

EMPA 104 blood (EMPA 111) cocoa (EMPA 112) mixed dirt (EMPA 116) tea (Krefeld 10 G) uninjured cotton (EMPA 222) wine (EMPA 114),

- detergent dosing:

first series: 5 g / l, second series: 8 g / l, ie. 5 x 20 = 100 g per wash, ie. 8 x 20 = 160 g per wash.

Method for determining the degree of soil and stain removal The calculation of the percent soil removal rate is made possible by photometric determinations (determination of the amount of light reflected by the fabric). Elrepho 2000 from Datacolor is used for this purpose.

The percentage of dirt removal is expressed by the equation:

Dirt removal rate (%) x 100 where:

A means the reflectance of the white reference sample,

B is the reflectance of the soiled reference sample; and

C means the reflectance of the soiled sample after washing.

The reflectance is determined using a blue trichromatic component without the effect of optical brighteners.

Number of measurements performed for each sample: 4, number of samples per wash: 2 number of washes: 3.

This is equivalent to 4 x 2 x 3 = 24 measurements for each type of dirt, each product and each concentration studied.

The anti-incrustation performance test in the washer was performed in a Schultess Super 6 De Luxe drum washer.

The following conditions were used in this test:

- cycle used: 60 ° C,

- total cycle time: 65 minutes; no prewash,

- number of cycles: 25 cumulative washes,

- water hardness: 21,2 ° French water hardness,

- test fabric: a reference band conforming precisely to the specification in NFT 73.600;

- washing machine load: 3 kilograms of third 100% cotton towels,

- detergent dosage: 5 g / l.

The test fabrics which have undergone 25 washes are then dried. It is then weighed and burned at 900 ° C. The weight percent ash, based on the weight of the initial test fabric, is then determined. The results of each test are shown in Table IV below.

Example 15

A detergent is prepared which is analogous to that of Example 14 except that the builder mixture zeolite 4A + the product of Example 14 + SokalanCP5 is replaced with the following builder mixture:

zeolite 4A part

- sprayed silicate

- light carbonate

- sodium sulphate

- Sokalan CP5 parts

4.8 part parts.

Test results Determining the soil removal rate and antiincrust test results are shown in Table IV.

Examples 16 to 18

The product of Example 8 is mixed in a Lodige M5G mixer with other ingredients to form dishwashing compositions. These compositions are shown in Table V. The compositions are tested in a domestic dishwasher whose water softener is not regenerated, and as a result provides hard water having a total hardness of 30 French water hardness. 10 cumulative washes of the original perfectly clean soda-lime glass plates are performed with each composition, with a concentration of 3 g / l of water used.

These plates are then subjected to a photometric measurement using a Gardner device identical to that used in Examples 1 to 5. The total amount of light L reflected by the sample is determined. If L lies between 4 and 7 the result is considered very good; the glass is clear. If L lies between 7 and 14, a slight veil can be observed on the glass.

The product of Example 8 is compared in a formulation close to a mixture of mixed sodium carbonate granules and Britsil H2O mixed granules (having a SiO ₂ / Na ₂ O = 2 ratio and containing 20% water, commercially available from Philadephia Quartz).

The results obtained are shown in Table V.

The use of the mixed granules of the example has been found to make it possible to reduce the amount of sodium citrate (which is expensive) and polyacrylate (which is not biodegradable).

Table III

Example 1 2 LABS 2 g / l wall granules 4 g / l 1 3 LABS 2 g / 1 carbonate 3 g / 1 R ₂ spray. 1 g / l Det EMPA cotton 19.27 17.63 Det EMPA PEC 24.52 23.13 Det WINE Cotton 19.20 19.49 Cumulative DET 62.99 60,24

Table IV Example 1 4 15 Det cotton 5 g / l 57.7 50.5 Det cotton 8 g / l 62.5 56.2 Det PEC 5 g / l 38.4 36.6 Det PEC 8 g / l 46.7 44.5 Det protein 5 g / L 42.6 46.6 Det protein 8 g / L 50.8 54.1 Bleaching 5 g / l 4 3,9 37.3 Bleaching 8 g / l 57.9 45.3

Table IV (continued)

Incrustation 5 g / l 0.69 0.85 General diameter 5 g / l 45.65 42.75 General diameter 8 g / l 54.47 50,02

Table V

Example 1 5 1 6 1 7 Mixed granules from Example 8 59 54 Mixed granulated sodium carbonate - - 31 Britsil H2O - - 17 Sodium citrate 1 7 20 25 Sodium polyacrylate MW. = 4500 4 5 5 Sodium sulphate 4 5 6 Nonionic surfactants 2 2 2 Perbori- monohydrate sodium tetanus 1 0 10 TAED 2 2 2 enzymes 2 2 2 L 5.3 5.2 5.2

Claims (4)

PATENT CLAIMS A builder agent for detergent compositions, characterized in that it is an alkali metal silicate, in particular sodium silicate or potassium silicate, containing at least 30% of the silicon atom in the form of a. Builder reagent according to claim 1, characterized in that it is composed of an alkali metal silicate, in particular sodium silicate or potassium silicate, containing at least 50% of the silicon atom in the form and Q 6. A builder agent according to claim 1 or 2, characterized in that it is constituted by an aqueous solution containing about 10 to 60% by weight of the dry matter of an alkali metal silicate, in particular sodium silicate or potassium silicate, having a SiCl 2 / ^ 2 O molar ratio of about 1. 6 to 3.5. A builder agent according to claim 1 or 2, characterized in that it is constituted by an aqueous solution containing about 10 to 60% by weight of the dry weight of alkali metal silicate, in particular sodium silicate or potassium silicate, having a molar ratio SiC 2 / O 2 which ranging from 1.6 to 3.5 absorbed in a particulate carrier which is inert to said silicate and / or adsorbed on such carrier, wherein the weight ratio of silicate dry matter / remaining silicate bound water ranges from 100/120 to 100 / 40th A builder reagent according to claim 4, characterized in that the carrier represents 55 to 95% by weight of the carried solution, expressed as dry matter. A builder agent according to claim 4 or 5, wherein said carrier is sodium carbonate, sodium sulfate, sodium borate, sodium perborate, sodium metasilicate, phosphate or polyphosphate such as sodium phosphate, sodium tripolyphosphate and the like, or a mixture thereof. salt. A process for the preparation of a builder reagent according to any one of claims 4 to 6, characterized in that it comprises adsorption and / or absorption in which a concentrated aqueous solution of an alkali metal silicate having a SiO ₂ / M ₂ O molar ratio of about 1.6 up to 3.5, with a dry matter content of about 10 to 60%, contacted with an inorganic carrier inert to said silicate, said carrier being present in an amount such that the amount of residual water bound to said silicate after adsorption and / or absorption corresponds to a silicate / water dry weight ratio bound to a silicate of about 100/120 to 100/40. 8. The method of claim 7 wherein said contacting is carried out by spraying said concentrated silicate onto the carrier in particulate form at a temperature of about 20 to 95 ° C. 9. The spherical mixed granules of alkali metal silicates and alkali metal carbonates which are obtained; in a way that is - an aqueous solution of alkali metal silicate or a mixture of alkali metal silicate and alkali metal carbonate is sprayed onto the rolling bed of the alkali metal carbonate particles moving in a rotary granulation apparatus, the particle velocity, the rolling bed thickness and the amount of solution to be sprayed fed per unit of time is selected such that each particle is in contact with the other particles converted into a plastic blend granule, whereupon subjected to the compaction granules obtained by compacting treatment, and - said compacted granules are dried to such an extent that the water content of the silicate bound corresponds to a silicate / water dry weight ratio of silicate bound equal to about 100/120 to 100/40. 10. Spherical mixed granules according to claim 9, characterized in that the solution to be sprayed on the basis of a silicate or a mixture of silicate and carbonate has a dry matter content of about 30 to 55% by weight, said alkali metal silicate having a SiC2 / O2 molar ratio. ssi to 3.5 and said carbonate may be present in an amount depending on the desired final product. Spherical mixed granules according to claim 9 or. 10 wherein the silicate-based solution or the silicate-carbonate mixture is sprayed at a temperature of about -20 to 95 ° C. 12th Spherical mixed granules according to any one of claims 9 to 11 11, characterized in that the rolling bed forming particles are based on an alkali metal carbonate having: - a mean particle diameter of about 10 to 150 micrometers, - a specific gravity of the unshelled filling of about 0,4 to 1,1 g / cm ^, a water content of about 0.05 to 0.4%, and - an insoluble content of about 5 to 100 mg / kg. Spherical mixed granules according to any one of claims 9 to 12 12, characterized in that the rolling-bed particles comprise less than 10% by weight of the mixed granules of particles of a type other than an alkali metal carbonate, said particles having a diameter and density close to the diameter and density of the alkali metal carbonate particles. Spherical mixed granules according to any one of claims 9 to 14 13, characterized in that the granulating device is a rotary granulator allowing the movement of particles in a thin layer. 15. Spherical mixed granules according to claim 14, characterized in that the rotary granulator is formed by a rotary plate. 16th Spherical drum. Mixed granules according to any one of claims 9 to 13, wherein the granulation device comprises Spherical mixed granules 16, wherein the particles move at a temperature of about one degree that the particles per ° C. claims 9 to Spherical ridges 17, marked with silicate or mixture / 15 to 200 based on carbon dioxide according to any one of the fact that the amount of the silicate-based and carbonate-based solution to be sprayed and the carbonate-based particles used correspond to a ratio of feed rate / feed rate equal to 0.2 to 0.8 l / kg where these values are expressed as sodium salts, Spherical mixed granules according to any one of claims 9 to 18, characterized in that the compacting operation is carried out at ambient temperature by rolling the mixed granules obtained in the granulation step in a rotary device. 20. Spherical mixed granules according to claim 19, characterized in that the compacting operation is carried out in a rotary drum. Spherical mixed granules according to any one of claims 9 to 21 20, characterized in that the mixed granules obtained after compacting are dried in a fluidized bed. 22. Spherical mixed granules according to any one of claims 9 to 22 21, characterized in that a small amount of liquid compounds which are commonly used in the detergent field are added by spraying with the mixed granules obtained after drying. 23. Spherical mixed granules based on alkali metal silicate and alkali metal carbonate, characterized in that they have: - a silicate content of about 8 to 38% by weight, the silicate having a SiC ^ / f ^O molar ratio of 1.6 to 3.5, - a carbonate content of about 47 to 87% by weight, - a water content of about 5 to 25% by weight, a specific gravity of the unstretched filling of about 0.7 to 1.5 g / cm @ 2; and - a mean particle diameter of about 0.4 to 1.8 mm with a log ₁ θ-standard. T 24. Spherical mixed granules of hydrated sodium silicate and sodium carbonate, characterized in that they have: - a silicate content of about 24 to 31% by weight, the silicate having a SiC> 2 / Na 2 O molar ratio of 1.8 to 2.6, - carbonate content of about 64 to 69% by weight, - water content of 12 to 20% by weight, a specific weight of the unstretched filling of about 0.7 to 1.5 g / cm @ 2, preferably about 0.8 to 1 g / cm @ 2; - a mean particle diameter of about 0.4 to 0.8 mm with a log θ standard deviation of 0.05 to 0.1; and a dissolution rate of 90% granules in water of less than 2 minutes and a dissolution rate of 95% granules in water of less than 4 minutes. A builder agent comprising spherical blend granules according to any one of claims 9 to 24. VJ Use of the builder agent according to claim 3 in powdered detergent compositions by spraying onto the powdered detergent at the bottom of the tower or on a mixture of detergent formulation ingredients, wherein the weight ratio of silicate dry / detergent powder or formulation is equal to 1/100 to 30/100 and weight. the silicate dry matter / residual silicate bound water ratio is also 100/120 to 100/40. Use of a builder reagent according to any one of the claims 4 to 8 and 25 in powdered dishwashing detergent compositions in an amount of 3 to 90% by weight of the silicate dry weight, based on the weight of the composition. Use of a builder agent according to any one of the claims 4 to 8 and > 25 in powdered detergent compositions for washing machines in an amount of 3 to 60% by weight of the silicate dry matter, based on the weight of the composition.