BG97549A - ACTIVE SUPPLEMENT FOR PERIPHERAL PREPARATIONS - Google Patents

Abstract

The active additive is intended for detergent compositions for washing machines and dishwashing machines. It comprises an aqueous solution of an alkali metal silicate, in particular sodium or potassium, in which the ratio of $u2/m2o is from 1.6 to 4, m being an alkali metal, and a mineral product inert with respect to the silicate in an amount of from 5 to 55% of the total weight, expressed as dry matter. The weight ratio of water bound to the silicate to the silicate, expressed as dry matter, is higher than or equal to 33/100, preferably 36/100.

Description

The object of the present hezr) composed of a solution of the invention is tonildler (alkali metal rich silicates rich in silicon atoms under

The form HajQ ^;

the composition of a mineral product inert with respect to silica. This builder is designed for detergent d ιί to make particular powdered laundry detergents and especially for washing machines or dishwashers.

The invention also relates to alkali metal hydrated silicates and granules with alkali metal carbonates.

• · · · · · · ·

By '' L1b1e1 '' (builder) is meant any _L- active additive that improves the surface properties of the detergent composition-active substances.

It is necessary for the builder to have a woofer called water softening used for washing. However, calcium and magnesium, which are present in water in the form of soluble salts, and in impurities in washing machines in complex forms that are more or less soluble, should be eliminated. The removal of calcium and magnesium can be accomplished either by complexation, under the form of soluble species, under the form of ion exchange, or by precipitation. When it comes to sedimentation, it must be controlled to avoid sedimentation in the washing machines or parts of the dishwashers.

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

It is also necessary for the builder to have an emulsifying effect of surfactants in relation to oily contaminants, a dispersing effect on:> pigment contamination, such as metal oxides, glaciers, silica, dust, humus, limestone. ...

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

It is also necessary for the builder to provide: favorable. ionic strength of the functionalities of the surfactant, in particular by increasing the size of the micelles.

It is also necessary for him to have fatty saponins and to increase the negative effects of fatty sores and to increase the negative ones. · · · · · · · · · · · · · · · · · · · · Surface charges of the textile surfaces ι on the surfaces of the particles of impurities. · · · · · ······

Silicates have long been considered as good exit excipients, but in reality there are fewer uses of tn in phosphate-free formulations for washing machines.

The most commonly used silicates in these cases are those which have a molar ratio of SlOa / ^ a ^ O in the range between

1.5 and 2.7. They constitute a commercial product ^g and was in the form of concentrated solutions with 35-4-5 tegg. '/ A> x moiety, either in the form of finely divided prahoobu gzen silicate and then pressed.

Commercial concentrated solutions of - if obtained from a completely amorphous silica gel, called vitreous and also called soluble glass

These soluble glasses were dissolved in 3c ia in a pressure autoclave at 14 ° C. In this way, organic solutions having a dry residue of the eye are obtained. to 4-5 wt.h. sa. silicate with a ratio of 2 and about 35 W. for a silicate with a ratio of 3.5.

The concentrated silica solutions were introduced into an aqueous suspension (sludge, slurry) containing npyrts with detergent components. The sludge is then dried by spray spray. silicate pulverized and co-dried with the remaining constituents, contains no more than 20 W. bonds. water relative to its dry content, even smaller>.

As for commercial powder, it is obtained by spray drying the concentrated solutions of glassy silicate; it is necessary to retain 19 to 22 parts by weight of water in relation to the final product in order to ensure good solubility of the product.

Ts

It has been found that when it is placed as a 1-3 g / l solution in myal Oani, this powdered cat, which contains only 1Φ-2 lb.wt.X of bound water (relative to the final product), has only weak properties on the bil per.

in fact, this dissolved powdered silicate gives many monomeric silicate species of formula Si (O)

where X is H or Na, which do not have a builder effect. These monomeric species cannot reactivate with each other to form polyanions unless the concentration of silica is at least 50 to 500 n / l and then slowly.

Such concentrations of silica as well as the slow kinetics of polymerization of the monomer species are incompatible

What is found for powder containing 20 to ££ Y.

chemically bound water (with respect to the final product) is, of course, true for compositions containing 20 W. silicate.

bound water (with respect to dry silicate) prepared by introducing a concentrated solution of silica into a slurry. **> ·>

after drying.

The Applicant of the present invention has found that when the silicate is an alkali metal is rich, the silicon atoms are in the form of <

a nd species obtained by diluting from 1 to polyanion3 jr / l in the mixing medium have a duration of action sufficient to play the role of a builder in the washing.

The expression of silicon atoms in the form a-O ^ and Qj is a way of showing the degree of bonding of silicon atoms between them; means that each silicon atom participates in two bonds -SX-O-S1-, with the other two bonds

ς>

have a -SX-O-X termination group, wherein X is an alkali metal or H; Q $ means that each silicon atom participates in three bonds -S1-O-S1-, with the free bond ending at

-SX-O-X.

Builders for a detergent composition, object of the present invention is characterized in that it is composed of an aqueous solution of alkali metal silicate, particularly potassium or sodium ,, with a molar ratio of SIO2 / H2 ° ^from P ^January E ^{pouring the residue of}

1.5 to h and a mineral product inert with respect to silica and miscible in silica solution, this product representing 5 to 55 X of the total weight in the dry state and the weight ratio of water bound to the silica / dry silicate greater than or equal to 33/100, preferably 36/100, where M is an alkali metal.

By inert is meant chemically inert.

Mineral products inert with respect to silica and compatible with the aqueous solution of silicates are preferably water-soluble, the following may be cited: sodium carbonate, sodium sulfate, sodium borate, sodium perborate, sodium metasilicate, Phosphate, or Phosphonates, such as trisodium phosphate, sodium tripolyphosphate ..... these products being present alone or in a mixture.

The use of products having detergent activity and in particular sodium carbonate is preferred.

The mineral product has from 5 to 55 (preferably from 5 to 55) of the total weight of the dry residue, i. of the sum of the weights of the solution, expressed as dry matter and mineral product.

The mineral product is introduced either directly into the aqueous solution of the alkali metal silica or on the water and after mixing in the aqueous solution of the alkali metal silica.

The eilder according to the invention can be in any structure (dust, granules ....) or unstructured

Form.

The silicate in question may have a molar ratio

In a preferred embodiment of the invention, the builder is preferably 10 to 35-50 wt. X. Of a dry residue of an alkali metal silicate, in particular sodium or potassium.

The concentrated alkali metal silicate solution used as a boiler is preferably obtained by dissolving soluble glasses in an autoclave in water at pressure and temperature and then optionally not; it can also be obtained by other dilute methods known, for example, by direct treatment of sand with concentrates by NMR soda caustic (sodium hydroxide).

it is established that:

- solution with -4-5 / dry glassy silicate content and a molar ratio of SlC ^ / Na ^ 0 = 2 contains ZH-Z of species, 51 / of Gfe species, 12Z of species Ql and 3X of species

QO

- solution with 35 /. dry residue and a ratio of 3.5 contains

The term silica-bound hydrogen refers to water from a carrier solution that is not attached to the mineral carrier, but in the form of crystalline hydrate.

The weight ratio of water remaining bound in silica / silicate expressed as dry matter should be greater or different than 33/100, preferably 30/100, which corresponds to the need for silicates to be in polyanionic forms. It is not difficult for the person skilled in the art to fix the upper limit of this ratio, and this limit of course corresponds to the limits to which the silicate can be maintained.

Free flowing flow in the Powder Farm, ie. applicable for washing. For example, the weight ratio of water remaining bound to silica / silicate, expressed as dry, should be less than or equal to 120/100.

The high content of silicate in the products according to the present invention enables the achievement of completely satisfactory anti-scale properties in the washing or washing machines.

The builder in question, when in unstructured form and in particular in solution, may be used by further atomizing on the outlet laundry dust in the case of atomisation installations or on the mixture of components of the laundry detergent in the case of dry mix, and so on to be absorbed by the powders. The resulting powder mixture, if necessary, is moderately dried in such a way that the weight ratio of water remaining bound to the silica / silicate expressed as dry matter remains greater than or equal to 33/100, preferably 30/100.

The amount of silica solution in the builder, in the solution that can be used, preferably corresponds to a dry silicate / washing powder by weight ratio of • · · ·

between 1/100 and 30/100, preferably »between 10/100 to it / ιοο.

When the Wilder According to the Employed: The Invention is Structured Form It can be prepared by contacting an aqueous solution (A) made up of a mixture of a concentrated aqueous solution of silicate ι a alkali metal (1) with a fashion ratio

SX

About between 1.6 and

4-, preferably between 1.6 and 3.5, and a mineral product (a condition wherein the mineral product is inert to the ratio of kata and compatible with the aqueous solution (1: and is a silo of 5 to wt. X of the total weight of the dry substance with compound ( B) having a composition identical to the above aqueous solution (A) in such a way that the weight ratio of silica / silicate bound water expressed as dry matter after mixing is greater than or equal to 33/100, for preferably 36/100.

In all that has been said here, unless otherwise stated M is an alkali metal.

the aqueous solution (A) is prepared by any of the known methods. It can be obtained by introducing the mineral product 'in the form of a threshold or liquid into the aqueous solution of silica.

Compound (B) with a composition dentic to aqueous solution (A) means any compound containing an alkali metal silicate and mineral product defined above, the mineral product representing 5 to 55 V. of the total weight expressed as dry. This compound (B) has a weight ratio of silica / silicate bound water expressed as dry matter greater than or equal to 33/100, preferably ze / yo.

• · · «· · .. ··· · ··· ···· ··· ····· ·· ·· ·· ··, compound (B) can be prepared by any of the the known ways. Thus, it can be obtained by drying a solution identical to the aqueous solution (A). It is preferable to control this drying in such a way as to maintain the desired amount of silica bound water, i. in such a way that the weight loss of the silica / silicate bound water expressed as dry matter is higher than or equal to 33/100, preferably 36/100.

Shi »·

In aqueous solution (A), the concentrated alkali metal silica aqueous solution preferably has a weight ratio of silica / silicate bound water expressed as dry matter to be greater than or equal to 33/100, preferably 36/100.

Contacting can be accomplished by the addition of, in particular, by spraying (A) onto (B) in any LODIGE type Rotary Mixer or in pelletizing devices (drum, disc ...). ., at temperatures between 20 and 95 ° C, preferably between 70 and 95 ° C. _{w The} mineral products which may be used are mentioned above.

the amount and concentration of the aqueous solution (A) that can be used is a function of the adsorption and / or adsorption capacity of the mineral products present in solution (A) and the compound (B) as a result of the silica present in solution (A) ) and compound (B), taking into account the possible possibility of the mineral products to form crystallizing hydrates, the amount of silica-free water can be in the form of a hydrate in the carrier and can be readily determined by ШW® ·· · · · · · · · · · · · · · · · · · · · · · ·

ΙΟ some of the known methods, for example by differential chemical analysis or quantitative X-ray diffraction. The water, optionally present in the carrier in non-hydrated Formulas, can be determined by suitable Physico-chemical methods (thermoporsimetry, thermogravimetry, proton NMR, IR).

The limits of the adsorption or adsorption capacity of mineral products can be determined by measuring the change in shear angle during shear as a function of the amount of silica solution added.

If necessary, a drying step may be applied after contacting (A) and (B), but this should be moderated so as to obtain the desired amounts of silica-related water.

Alkali metal silica solutions under adsorbed and / or absorbed Form on alkali metal carbonate, and which are in the form of the co-granules of the hydrated alkali metal silicate and the alkali metal carbonate are the builders of the present invention with particularly good properties.

These co-granulates of the hydrated alkali metal silicates and of the alkali metal carbonates are characterized in that they can be obtained according to a method comprising the following steps:

a) spraying an aqueous solution consisting of a mixture of an aqueous solution of an alkali metal silicate with a molar ratio of 1.6 and preferably between β.β and 3.5 and an alkali metal carbonate, this carbonate being 5 to 55% by weight expressed as dry on a layer of passing particles having a composition identical to the atomized mixture, pass through a rotary granulation device, whereby

c: the particle crossing point, thickness a. of the layer and the flow rate of the nebulized solution are such that a green particle becomes a plastic co-granulate by contacting other particles,

6) possibly drying the co-groups using ιθηη in step (A), applying these steps in such a way that the final weight ratio is water bound to silicate? / silicate, expressed as a dry matter, greater than or equal to 33/100, preferably 36/100.

These co-granulates can be used: as a simple agent and capable of providing strength · cat and carbonate in detergent compositions.

Particles of the composition identical to the atomized mixture are understood to mean particles comprising an alkali metal silicate and an alkali metal carbonate, representing 5 to 55. cm total weight expressed as dry matter. These hg: tics preferably have a weight ratio of water having a silica / silicate bond expressed as dry matter: yours greater than or equal to 33/100, preferably 3b / yo, • M · '' ''

These particles can be obtained by any of the known methods.

In particular, they can be obtained by drying an aqueous solution identical to the silicate and carbonate of the above-mentioned alkali metal. This drying is controlled in such a way as to maintain the desired amount of silica bound water, i. weight ratio of water © becoming bonded to silica / silicate expressed as a dry matter greater than or equal to 33/100, preferably 36/100.

The particle layer of the composition is identical to the mixture for • · · · · · · · · · · · · · · · · · · · · · · · · · · · · · The spray can also be obtained by going from? a dry mixture of carbonate and silicate by weight of carbonate / silicate identical to the nebulizer solution until complete refinement of this layer from the resulting constituents; you (recycling).

In an aqueous solution composed of a silicate / carbonate mixture, the concentrated aqueous solution of the alkali metal silica preferably has a weight ratio of water remaining bound to the silica / silicate expressed as a dry matter greater than or equal to 33/100, preferably 36 / 100.

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

Preferably, between the steps (A) and (B), the resulting coronalates from step (A) are subjected to compaction.

According to a preferred embodiment of the invention, the silica solution used to prepare the co-granulates has a dry silica residue in the range of 10 to 60, preferably 35 to 50 κ.

The aqueous solution based on the silicate / carbonate mixture is sprayed at a temperature between ao and preferably between TO and C; this may be facilitated by the simultaneous introduction (for example with a bi-fluid nozzle) of pressurized air at a temperature of the same order.

The carbonates used can be of ordinary quality. Carbonates which are readily soluble and have an increased adsorption / absorption capacity are preferred.

Along with the carbonaceous particles, there may be other amounts (less than 10 parts by weight and by weight of the co-agglomerates) of other particles, such as anti-precipitation polymers (carboxymethylcellulose ...), enzymes, polyacrylates ... commonly used in the purification field a technique having a diameter and density close to that of the parts of the yarbiate / silicate mixture.

The device for conducting the co-granulation by pulverization: the wound can be any kind of rotary device of the types, they are: rotary disks, device for receiving dragees, rotary drum, mixer-pranulator ...

One preferred method of obtaining co-granulates is in the use of a rotary granulator allowing the passage of the particles into a thin layer. Devices for producing drages with a pivot axis inclined with respect to the n horizontal at an angle greater than Ξ. &Quot; and preferably greater than -C-CP are particularly suitable; their geometry ms be too different: cross cone, flat, stepped, a combination of the three shapes.

In chi, Another preferred method of producing co-granulates is to use a rotary drum whose angle of rotation is at least 3Z and preferably 5Z.

Erasers based on the carbonate / silicate mixture pass at a temperature in the order of 15 to 2Ops, preferably from 15 to ιεο 3c and most commonly between 15 and the amounts of the solution based on the mesh silicate / carbonate spray and particulate matter. the base of the silica / carbonate mixture corresponds to a liquid / particle flow rate (wetting ratio) of 0.05 to o, l ^x kg, preferably 0.1 to 0.5 l / kg and most often of 0.15 to

:>, h l / η, these values being expressed in k; it salts the sodium flow rate of the nebulized solution, the rate of passage ί x particles as well as the thickness of the layer of particles are suchE1 that each particle absorbs the liquid and agglomerates with other particles with which it comes into contact so that ethical granulate, not porridge.

the particle transfer scales and the thickness of the layer t are regulated by the flow rate of introduction of the particles into the device; ictboto for granulation and after-day characteristics.

The residence time of the particles in a disk or drum unit is typically between 15 and 40 minutes.

It is within the power of each person skilled in the art, depending on the starting materials, to adapt the apparatus used to obtain the desired product; namely, a receiving device for dragees:

geometry (truncated cone, flat or stepped or b 15ination of the three shapes),

W dimensions (height, diameter), tilt angle, rotation speed, relative position of the power supply; .they have solid and liquid! parts.

For ba; aban:

geometry (cylinder diameter), angle of inclination,

- rotation speed,

- Charging the cylinder relative to the position of the solid and liquid feeds is a matter of parts.

The sealing ration can be carried out at room temperature by passing the granules obtained in the step of granulation through a rotary device.

This device is preferred to be separate from that of the granulation.

During the compaction step, it can conveniently be carried out by inserting and stopping the granules in a rotating

What a * »drum. The inclination angle of the latter is at least 3Z, preferably at least 5Z. The size of this drum, its rotational speed and the residence time of the co-granules depend on the desired density; the dwell time is usually between ΞΟ min and? hours, preferably between 90 minutes and 90 minutes.

Mixer granulators are also suitable for the compaction process.

Co-granulation and compaction bunches can also be made in the same device, for example, in a step-visible dragee device, the compaction of co-granulates being achieved by passing them ** through the last steps of the apparatus; in addition, these two operations can be performed in a two-section drum.

The compacted co-granulates thus obtained are dried in some known manner. A particularly successful method is fluidized bed drying using air and at a temperature between 4-0 and 9 <P C, preferably between 60 and S-F ⁶ C. This pebble is carried out for a time which is a function of the the air, the water content of the granules exiting the granulation apparatus and the desired water content of the dried granules as well as the fluidization conditions; these conditions can be adapted by any one specification depending on the desired product; the granulates based on hydrated sodium and sodium carbonate silicates according to the invention and which can be obtained according to the method described above, are intended for detergent compositions for washing machines and dishwashers and are typically characterized by having:

-silicate of alkali metal, in particular sodium or potassium in a molar ratio of SlOa / fet ^ O between 1.6 ml D-adsorbed and / or adsorbed on alkali metal carbonate, this carbonate being 5 to 65 X by weight of silica adsorbed and / or absorbed by the carbon and the weight ratio of the water remaining bound to the silica / silicate expressed kg then the dry matter is greater than or equal to 53/100, preferably

36/100.

- Bulk density without compaction from O, At to

1.6 g / cm ³ , preferably 0.5 to 1.5 g / cm ³ and most commonly

FROM 0.7 ': · UP TO 1

Τ '/ Cl ·? , jab

-Middle ί from O, At diameter (in terms of percentage of passed hour the 1.6 mm, preferably from 0.5 to 0.6 mm .t second with no o ^d

Preferably the weight ratio of water remaining bound to silica / silicate expressed as dry matter should be less than or equal to 120/100.

The method described above, including co-granulation / compaction / drying, allows the preparation of co-granulates based on hydrated alkali metal silicates and carbonates of the granulates according to the invention, respectively, in less than 3 minutes and 5 minutes.

• · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

IT year dissolution rate up to 9OZ or up to 95 / in water the time required to dissolve 90 or 95 / cm3 of product at a concentration of 35 τ '/ n in water at r.

When structured (powder, granulate ...), the builder according to the invention is used in detergent compositions for dishwasher detergents in an amount of from 3 to 90% by weight, preferably from 3 to 10% by weight, of the compositions in question; the amounts used for the compositions intended for the linear lines are from 3 to 60 wt.%, preferably from 3 to iiO wt., and from the compositions in question (these quantities are expressed as weight of dry silicate with respect to the weight of the composition) .

In addition to the presenter of the present invention, at least one surfactant in an amount of from 8 to 20, preferably from 10 to 15, by weight of said composition is present in the laundry composition.

Among these surfactants may be queried:

-Anionic surfactants such as alkali metal soaps (alkali salts: a fatty acids with

C2U alkaline sulfonates (alkylbenzenesulfonate

C / z Ciz-C # c®-g,, alkylsul Phonates with oxyethylated and

Ce-CPe, sulfated fatty alcohols with * £, oxyethylated and

Cs-C, 3 Sulphated Alkylphenols with, Alkaline Sulphosuccinate

C, ₂ -Cfjt, (Fos alkyl alkyl succinate fe <≤ R- ") ...

non-ionic surfactants of the type

C ₆ -? 2 polyoxyethylated alkylPhenols with? Oxyethylated aliphatic alcohols with%, ethylene oxide block copolymers of propylene oxide, carboxyamides, optionally polyoxyethylated? · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

other ingredients such as:

- builders of the type:

- Phosphates, up to 25 /. of the total weight of the composition,

-Zeolytes up to about 4-0 / of total weight of the composition, -Nat carbonate up to about 60 / of total weight of the composition, nitrile acetic acid up to 1OZ - t total weight of the composition,-citric acid, tartaric acid up to 20 / the total weight of the composition, the total volume of the builder being from 0.2 to SOZ, preferably from 20 to 4-5 / s, the total weight of the detergent composition in question,

-Bleaching agents of the type> borates, percarbonates, chlc rhizocyanurates, Ν, Ν, Ν ', м'-methadethylethylenediamine (TAED) up to about 30 / of the total weight of the detergent composition,

anti-inflammatory agents of the type ι ί carboxymethylcellulose, methylcellulose in an amount up to 5 / of the total weight of the detergent composition,

- anti-boiling agents of the type of copolymers of acrylic acid and maleic anhydride in an amount up to 1ΟΖ of the total weight of the detergent composition,

- Sodium sulphate fillers for powder detergents in an amount up to 50 / of the total weight of detergent19.

The following examples illustrate the invention without limitation.

EXAMPLE 1

Builder synthesis:

Products used in synthesis:

Sodium silicate: Molar ratio solution *

! SlOa HjNa ₂ 0 = 2.6

Dry residue: 45 wt /

Density 1,500 Distribution of polyanionic species as a percentage of silicon): ςβ _β = 0.6 /., Qi = 6.2 /., Og B = Θ3 X, = 1OX.

-Sodium carbonate: Anhydrous powder

Bulk density without compaction:

1.1 g / cm 3

Granulometric composition: <350 = 0.5 mm

Synthesis:

** The pre-dissolved sodium carbonate is added with stirring to the sodium carbonate solution heated to eo <C. The addition of water to sodium carbonate in this case makes it possible to work with a mixed solution whose dry residue is identical to the dry residue of the silica stock solution. Mixing is carried out in such a way that the sodium carbonate represents 50% by weight of the total weight of the silica silica and the carbonate expressed as dry.

the mixed solution was dried in a thin layer dryer at 2 ° C for 20 hours. The resulting solid was then ground into a Fojrplex mill. The last stage is

consists of drying in a fluid bed at 30-40 C so as to form a solid with the following composition;

sodium carbonate 3 x of the total weight of carbonate and silica expressed as dry weight.

The weight ratio of water remained bound to silicaTa _z : ikat expressed as dry is 49.7 / 100.

The product has the following properties

Bulk density without compaction; O, & g / cm ³

Granometric composition: 6.50 = 0.5 mm, <3.10 = 0.1 mm, cl 90 = 1 mm

Solubility; less than 4 minutes to dissolve 99 / · of the product (conductometric measurement of the aqueous solution of the product at a concentration of 3 g> / l at 2g ^is C) 'calcium-forming complex; 197 mg CaCO3 per gram of anhydrous product. This capacity is calculated by measuring the residual calcium concentration over a period of 15 min, with the determination product being introduced at the moment -t = O in a solution with a known mud concentration (b Ferrous solution with pH 10).

Example_2

Obtaining the granule:

The following products are used:

Sodium silicate: Molar ratio solution

SlOe / ^ a ^ 0 = 2.0

Dry residue: 45.5 wt

Density 1,540 g / cm ³

Powdered silicate: molar ratio · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

Dry residue: weight DENSITY 0.55 g / cm ³ Granulometric composition: <150 = 0.12 mm.

-Sodium carbonate: a light solution

Bulk density o, is · g / cm ³ Granulometric joint: 0.50 = 0.12 mm. a 36 wt.% solution of the carbonate carbonate solution is prepared by mixing the carbonate solution in a silicate solution with a ratio of 2. The dry residue of the mixture thus obtained: the solution is 37.7 37.

The granulation of this solution is carried out in a drum with a length of 1300 mm and a diameter of 500 mm, which rotates at 20 rpm. Granulation is initiated by starting from a starting joint composed of a crushed mixture of light carbonate and powdered silicate at a ratio of 2. The composition of carbon / w / silicate of this mixture is the same as the mixed solution. The granulation is carried out in the first part of the drum where the solution is sprayed through an irrigator onto the powder with it. Drying is carried out in the second part of the drum, equipped with lifting dippers and hot air balloons. ** Granulation, compaction and drying are also carried out in the same apparatus. The product drunk from the drum is partially recycled into the head of the drum after grinding and sieving a fraction of 0.2-1.25 mm. Thus, in the established mode, i.e. When the base of the base layer is completely updated with the newops lumen products, the granulation parameters are as follows:

- supply with mixed solution 6 up to l / m

- Dust supply (recycling) 50 kg / h wetting

0.12 TO ODL / KG

d.2

- air flow rate for drying but up to 120 m ³ / h

- drying air temperature 105-11QOC

- average residence time in the drum 30-40 min.

In this way, co-ordinates are obtained with the following characteristics:

- dry carbonate / silicate ratio = ze / en

- silica / silicate bound water content, expressed as dry matter = 51/100

- Bulk density without compaction: 0.59 g / cm ³ Granulometric composition: 650 = Ο, · 4 · 5 mm, 695 = o, mm with deviation of 1 »^^ type 0.37.

The granules obtained have the following dissolution times:

-9ΟΖ (wt ·) of the product dissolve in 50 sec.

(aqueous solution 35 ppm at £ (^ C)

-95Ζ (w / w) of the product dissolved in 67 sec. (water solution 35 p / l at 2 ° C)

-99Z (wt.) Of the product dissolved for 1544 sec. (aqueous solution 35 τ '/ l at 2 (^ 0' W) For comparison, the ordinary dry mixture of carbonate and powdered silicate used at the beginning of the process which is not the subject of the present invention shows the following dissolution times:

-9ΟΖ (wt.) FROM the product does dissolves for 55 sec. (aqueous solution 35 Τ '/ L at gf ° C) -95Ζ (wt.) by the product does dissolve for 1O sec. (vo- day solution 35 r / l at g (£ * C) -99Ζ download) by the product does dissolved for 256 sec. (vo-

day gaseous 35 r / l at 2 <^ ^ΰ Ο

1: shrink capacity max 24: -49 mg

CaCCg ca gram anhydrous product. This capacity was calculated as Example 1.

Example 3

Getting co-granulates:

The pelletizing method is the same as in the example, but uranium: the lator works on an open cycle, i.e. τ Ή is charged with a dry powdered carbonate / silicate mixture and a saline solution, but • h. without recycling the resulting product. There is also some yum (dry drying).

the granulation parameters are as follows:

- supply with mixed solution 6 ppm

- power supply is dust (recycling) 3 <kg / h

-the degree of wetting 0 2 to 0.2 7 l / kg

- air flow rate for drying a:> up to 120 mH / h

- air temperature for drying

- average residence time in the drum zone - ^ i-O min.

In this way, a subgroup ^d is obtained with the following characteristics:

- dry carbonate / silicate ratio =? n / 63

- silica / silicate bound water content, expressed as dry matter = ^ -2 / 100

- Bulk density without compaction:?, 54 g / cm ³

Granulometric composition: 050 - 0.57 mm, 0.95 = 0.76 mm with deviation from ^TYPE °> ^{1 g} ·

The granules obtained have the following times of loading:

-9OI (wt.) Of the product dissolved in 55 sec. (aqueous solution 35 Τ '/ l at 20 ° C) · · · · · · · · · · · · · · · · · · · · · ·

Al · _x '95Z ('Ter'Ji.) Dissolved in 122 sec. (55 g / l aqueous solution at g &lt; 0 &gt; C)

-99 / (wt.) Dissolved in 500 sec. (55 g / l aqueous solution at 2 (^ 0)

These co-granulates are mixed dry with the following additives to obtain a composition for washing machines:

Laundry powder composition ______ parts by weight

granulate

oXalan CP5

β

(copolymer

(amorphous silico-apuminate

TAED

LAB

(enzyme production

NEW)

Tlnopal DMSX

SOP antifoam

C>.

ε

carboxymethyl cellulose

The test for the ability to remove frostbite is carried out in a washing machine FOM τι.

V / ASCATOR.

The terms of. the tests are as follows:

-used cycle: 60 ° C

- total cycle duration: minutes; without warning

- number of cycles: 3 per wash

- water hardness: 32 French hydrostimetric degrees

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

-Tested fabrics: Attach two washcloths of each of the following fabrics to each washcloth:

Gray Cotton:

Gray Polyester / Cotton:

Protein stains:

oxidizing spots:

Tes + .- Fabrlc Krefeld IOC IEC 106 EMPA ΙΟΙ

Test-Fabric

Krefeld 20 C

EMFA 1044 ·

BLOOD (EMPA 111)

Cocoa (EMPA 112)

Mixture (EMPA 116)

Tea (Krefeld Yu <3)

Ecru cotton (EMFA222)

WINE (EMPA 11-44-) • · · · · · · · · · · · · · · · · · · · · · · · · · · ·

Ξ6

Dosage and detergent:

1st batch: 5 m / l or 5 x 20 = 100 g ¹ n; laundry

Other series: is w / l or 6 x 20 = 100 g · ng wash

Method for determining the removal of fatigue: titles and spots

Photometric measurements (measurement of the amount of light reflected from the fabric) allow <to calculate the percentage of removal of pollution. Here. this is the ELREFHO 2000 machine manufactured by DATACALOR.

The removal of contamination is pronounced; Formula Statement:

z-but removal = C-B χ 100

A-B where A = reflection from a white witness sample B = reflection from a contaminated sample witness <o = reflection from a contaminated sample after taking

Reflections are determined using tr: chromatic blue without optical brightening.

Number of sample measurements taken

Number of laundry samples = 2

Laundry count = 3 or -4 x 2 x 3 = 24 measurements of contamination, product and concentration tested.

Anti-boiling tests are conducted with the bi oxy drum machine SCHULTESS SUPER is DE LUXE.

The test conditions are as follows:

-used cycle: 60 ° C

- total cycle duration: 65 heard; without warning

number of cycles: 25 washings ·· ·· · · ································ ·· ·· ··

- water hardness: 21.2 French hydrotimetric degrees - used fabrics: testimonial tape that corresponds exactly to the speciFisation of stamdaart NFT 73.600

- quantity of laundry: 3 kg of fluffy wool 1OOZ cotton - quantity of detergent: 5 g l.

the samples underwent 25 washes were dried, weighed and reduced to 90 & c.

Z is determined by the weight of the ash n> ratio of the weight of the initial samples.

Separate test results are presented in a table. I.

comparative example of art

Receiving co-granulates:

The granulation system-ι ι is a drum rotating -4.0 rpm identical to that described in for: p 2. The outlet diaphragm is adjusted in such a way that the time of the residual particle is between 15 and 20 min.

The drum! m is continuously fed at a rate of 37 kg / h of powdered carbonate having the same characteristics as that of Example 2.

This powdered carbonate was rotated in the drum, with auxiliary air at a temperature of about ° C using a bifluid nozzle flat: a lava located in the first third of the drum was sprayed with a silicate solution identical to that of Example 2 at 's with a flow rate of 1 © l / h.

The co-granulate output from the drum is at room temperature and has a density of 0.56 g / cm ³ .

· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

The co-granulate is compacted continuously for 1 hour in a rotary drum with a smooth rod and a diameter of 500 mm, length 13 00 mm and an angle of 5 7.

The speed of rotation of the drum is 2 <rpm.

The granulate thus obtained is dried in a bubbling layer: a temperature of the order of 59 ° C (the fluidization temperature of the fluid for a period of 15 min.

The dry product has the following characteristics:

- ratio expressed as dry matter <carbonate / silicate = 66/34

- strength content of water; ata / silicate expressed as dry matter = 51/100

Complexing capacity of potassium -p 2S5 mg CaSOd per grg-ι anhydrous product. This capacity is calculated as in Example 1.

The granulate has excellent storage behavior.

To these agglomulates are added when mixed with additives so as to obtain a washing machine composition identical to the Het described in Example N- (except for the granules).

Dirt and scale removal tests have also been carried out with thickened perylene.

Result: these are presented in Table 1.

• · • · · · · · · · ·

Example of

Comparative example

Scale 5 p / l

3.72

2.88

Laundry results

gray cotton 5G / L 43% 32,2 3 2,9 gray cotton 8G / L W'c 4-7 4-1,9 gray cotton 5G / L 60 ° C 51,4 49 gray cotton 8g / l 56,3 54,8

4,6,73 4-4-, 65

Polyester / gray cotton bg / l <a ^ o ^yu s 39,2 3 5,3 Polyester / gray cotton 8G / L p 56.1 5 Oh. 1 Halfpeter / gray cotton 5G- / L 66 p 56,8 5 5.7 Polyester / gray cotton 8G / L 66 ° C 65,4 6 2.3

54-, 38 50.85

Protein stains 5 p / l ^ 0 * C. 58,8 3 4,8 Protein stains 6 g / l 99 ° 46,3 4 0.2 Protein stains 5 p / l $ 0 ° o 50.5 5 1 Protein stains 8 g · / l 6 $ ^Λ ο 58,8 5 6.4

4-6.58 4-5.60

Oxidizing se stains 5G / L 42.1 4 2,1 oxidizing se stains bg / l ^ ^is c 59.5 5 5 Oxidizing se stains 5G / L ^With 75,7 7 2.8 Oxidizing se stains 8G / L bb * s 63,8 82

Overall result

6 9.93

55.67 5 2.76

Claims (14)

kBilder for detergent compositions, characterized in that it is composed of an aqueous χ solution of an alkali metal silicate with a molar ratio of SiO ^ / f> θ between 1,6 and 4 and a mineral product inert with respect to silica and compatible with the force solution in question: ata, with this product representing from 5 to 55 X of the total ego expressed as * dry matter and the weight ratio at yes bound with silica / silicate, expressed as dry matter <gvo is greater than or equal to 33/100, preferably 35/100, where M is an alkali metal. D. Bilder according to claim 1, characterized in that the mineral product is sodium carbonate, sodium sulphate, sodium borate, sodium perborate, sodium: eu metasilicate, Phosphates or poly phosphates such as trisodium phosphate, sodium tripoly phosphate products can be used alone or in a mixture. Builder ' ¹ according to claim 1 or 2, characterized in that the mineral product represents 20 to 4-0 X of the total weight, expressed as dry matter. Bipder according to any one of the preceding claims, characterized in that the aqueous solution ι and the alkali metal silica has a dry residual force: at between 1O and 60 x, preferably between 35 and 50 X. m / eilder according to any one of the preceding claims, characterized in that the weight ratio of water remaining bound to the silica / silicate expressed as dry matter is less than or equal to 120/100. f. A builder according to any of the preceding claims, · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · 31, characterized in that the molar ratio SlOg / ^ ° is between 1.6 and 3, 5 and M represents an alkali metal. .7. Co-granulates of hydrated alkali metal silicates and alkali metal carbonates, characterized in that they can be prepared according to a method comprising the following steps: a) spraying an aqueous solution composed of a mixture of molar ratio W silicate alkali metal aqueous solution carbonate alkali metal having this total weight expressed as dry on moving 3.5 px by 5 to 55 X se layer time tics having a composition identical to the atomized mixture passing through a rotary granulation device, wherein the rate of passage of the particles, the thickness of the moving layer and the flow rate of the atomized solution are such that each particle becomes a plastic co-particle, contacting other particles , (b) optionally drying the co-granulates obtained in step (a), the steps being carried out in such a way that the weight ratio of silica / silicate bound water expressed as dryness is greater than or equal to 33/100, preferably 36/100, where M is an alkali metal. Co-granulates according to claim 7, characterized in that the silicate is the alkali metal and the carbonate of the alkali metal are those of sodium or potassium and preferably those of sodium. Co-granulates according to claims 7 or 8, characterized in that the co-granulates obtained in step (a) are subjected to compaction between steps (a) and (O). Co-granulates according to any one of claims 7 to 10 · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · 9, characterized in that the silica solution has a dry silicate residue from 1O to 60 7. preferably from 35 to 50 I. 11. Co-granulates according to any one of grades 7 to 10, characterized in that step (a) c <is carried out at a temperature between 20 and 9 ^^ 0. 12. Co-granulates according to any one of grades 7 to 11, characterized in that the particles: a composition identical to the atomized mixture are obtained by drying a solution identical to the aqueous solution in question, composed of silicate and alkali metal carbonate. Co-granulate according to any one of claims 7 to 12, characterized in that the pelletizing device is a rotary pelletizer allowing the mastic to be thinly bonded. 14. Co-granulates according to claim 13, characterized in that the rotary granulator is a ycTj unit for producing dragees. 15. The nil of zero according to any one of the grades 7 through W is characterized in that the granulation device is of a drum type. 16. Compensation for any of the grades 7 through 16, characterized in that the particles of the composition identical to the spray mixture pass at a temperature between 15 and εοφ′α. 17. Compensation for any of the claims 7 through 16, characterized in that the amounts of the solution solution based on the silicate / carbonate mixture for pulverisation and the particles based on the silicate / carbonate mixture correspond to the ratio of flow rate to liquid / part flow rate; ; 0.05 to 0.3 l / eg, preferably from 0.1 to 0.5 l / kg, these values being expressed as sodium salts. Co-granulate according to any one of claims 7 to 17, characterized in that the compaction is carried out at room temperature by rotation in the rotary device of the granules obtained in step (a). 19. Spherical co-granulates of the Hydrated Force Phase of alkali metals and alkali metal carbonates, characterized in that they have: - alkali metal silicate, in particular sodium or potassium molar ratio of wounds and / or adsorbed on alkali metal carbonate, which represents from 5 to 55 X of the weight of silica adsorbed and / or absorbed by the carbon and weight ratio of water bound with silica / silicate expressed as a dry matter greater than or equal to 33/100, preferably 36/100, - a bulk density without compaction between about 0 and 1.5 g / cm3, preferably between 0.5 and 1.5 g / cm 3? and especially between 0.75 and 1 n / s - an average diameter of O. ^ to 1.3 mm, preferably of 0.5 to O.S mm with a deviation of 1m ^ type from 0.02 to aboutb, preferably from 0.05 to 0.3.