JP2745400B2 - Spherical co-granules based on hydrated alkali metal silicates and alkali metal carbonates - Google Patents

Abstract

"Builder" agent, for a detergent composition, consisting of an aqueous solution of an alkali metal silicate, in particular of sodium or potassium, with an SiO2/M2O molar ratio of the order of 1.6 to 4, and of an inorganic product, inert with respect to the silicate, the said inorganic product representing from 5 to less than 55 % of the total weight expressed on a dry basis and the remaining water in combination with the silicate/silicate expressed on a dry basis ratio by weight being greater than or equal to 33/100, preferably greater than or equal to 36/100. Use of this builder agent in detergent compositions, more particularly in powder detergent compositions, in particular for washing machines and dishwashers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cogranulate of an alkali metal silicate hydrate and an alkali metal carbonate useful as a builder of a detergent composition and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION "Builder" means an active adjuvant that improves the performance of a surfactant in a detergent composition. The builder must have what is known as a "softening" effect on the water used for cleaning. It must therefore remove calcium and magnesium which are present in water in the form of soluble salts and in the soil of linen products in a more or less soluble complex form. Removal of calcium and magnesium can be effected by complexation in the form of soluble species or by ion exchange or by precipitation. If settling is involved, this must be controlled to avoid the formation of deposits on linen products or components of the washing machine.
This precipitation control is obtained using a water-soluble polymer having an affinity for calcium and magnesium in particular.

[0003] Builders are also concerned with emulsifying effects of surfactants on fat stains by using metal oxides, clay, silica,
A dispersing effect on "pigment" soils such as various dusts, humus, limestone, soot, etc. must be added. This dispersing action is generally obtained by the presence of polyanions that contribute to a high density of negative charges at the interface.

[0004] The builder must also contribute to the ionic strength which enhances the activity of the surfactant, especially by increasing the size of the micelles. It must also provide OH ^- ions for saponification of fats and to increase the negative surface charge of textile surfaces and particulate soils.

[0005] Silicates have long been recognized as good detergent adjuvants, but are now rarely used in phosphorus-free compositions for washing machines. Silicates most widely used in this application, SiO ₂ of 1.6 to 2.7
/ Na ₂ O molar ratio. These are 35
It is sold either in the form of a concentrated solution at an approximate concentration of ~ 45 wt% solids content or in the form of a spray dried and optionally compressed silicate powder.

[0006] Concentrated commercial solutions are in most cases made from so-called "glassy", completely amorphous silicates (also known as "soluble glasses").
These soluble glasses are available in autoclaves for 14 hours.
It is made water-soluble under pressure at 0 ° C. A commercial solution is thus obtained having a solids content of about 45% by weight for the silicate of ratio 2 and about 35% by weight for the silicate of ratio 3.5.

The concentrated silicate solution is introduced by the formulator of the cleaning powder into an aqueous suspension (slurry) containing the other components of the cleaning powder. The slurry is then spray dried. The silicate spray-dried with the other ingredients,
It contains about 25% or less bound water, based on its dry weight.

For commercial silicate powder, this is
It is obtained by spray drying a concentrated aqueous solution of a vitreous silicate. To ensure good solubility of the final product, 19 to 22% by weight of water must be retained with respect to the product.

The silicate powder, which contains 19 to 22% by weight of bound water, based on the final product, contains 1 to 3
When dissolved in the washing bath at a rate of g / l, it was found to have weak builder properties. In fact, this dissolved silicate powder is essentially of the formula Si (OX) ₄ (where X represents H or Na) without any builder action
Of the monomeric silicic acid species. Such monomeric species can combine together to form polyanions only when the silicate concentration is at least 50-500 g / l, and so gradually. Such silicate concentrations and slow reaction rates of the monomer species are not compatible with washing machine washing conditions and times.

What has been found in the case of powders containing 19 to 22% of chemically bound water (based on the end product) is, of course, the preparation by introducing a concentrated silicate solution into the slurry and then drying. The same is true for formulations containing silicate with about 25% bound water (based on dry silicate).

Here, in the present invention, when the alkali metal silicate in the solution state is rich in Q ₂ and Q ₃ forms of silicon atoms, these species present in the form of polyanions are eliminated in the cleaning medium by 1%. When diluted to ３3 g / l, they were found to have a long enough life to act as a builder in detergents.

The expression “silicon atom in the form of Q ₂ and Q ₃ ”
It indicates the degree of bonding between silicon atoms. The expression "Q
₂ "means that each silicon atom participates in two --Si--O--Si-- bonds and the remaining two bonds are --Si--O--X ends, where X is an alkali metal or H. Means The expression “Q ₃ ” means that each silicon atom has three
-O-Si- bonds are involved and the remaining bonds are -Si-
It means that it is OX terminal.

The builder for a detergent composition which constitutes the above object is an alkali metal (particularly sodium or sodium) having a SiO ₂ / M ₂ O molar ratio of about 1.6 to 4 (where M represents an alkali metal). An aqueous solution of (potassium) silicate and an inorganic compound which is inert to the silicate and is miscible in the silicate solution, and the inorganic compound has a total weight of 5 to 55% on a dry basis. Characterized by a water / silicate weight ratio of less than 33% by weight and remaining bound to the silicate, expressed on a dry basis, on a dry basis.

[0014]

The spherical cogranules based on hydrated alkali metal silicates and alkali metal carbonates according to the invention are: .
Alkali metal silicates having a SiO ₂ / M ₂ O molar ratio of about 6-4 (the carbonate accounts for less than 5-55% of the weight of the adsorption and / or absorbed silicate by salt carbonate acid)
Wherein the weight ratio of water / silicate still bound to the silicate on a dry basis is 33/100 or more, a bulk density of about 0.4 to 1.5 g / cm ³ , A spherical cogranular material characterized by having a median particle size of about 0.4 to 1.8 mm when log ₁₀ (standard deviation) is from 0.02 to 0.5.

[0015]

DETAILED DESCRIPTION OF THE INVENTION The term "inert" means chemically inert. The inorganic compound inert to the silicate and miscible in the aqueous solution of the silicate is preferably water-soluble. Examples of these compounds include, in particular, phosphates or tripolyphosphates such as sodium carbonate, sodium sulfate, sodium borate, sodium perborate, sodium metasilicate, trisodium phosphate and sodium tripolyphosphate, and These compounds exist alone or as a mixture with one another. Preference is given to using compounds having a detergency, in particular sodium carbonate.

The inorganic compound is less than 5 to 55%, preferably less than 20 to 40% of the total weight of the inorganic compound on a dry basis, that is, the total weight of the solution and the inorganic compound on a dry basis.
Account for%. The inorganic compound is introduced directly into the aqueous solution of the alkali metal silicate or is introduced into water and subsequently mixed with the aqueous solution of the alkali metal silicate.

The builder according to the invention can be shaped in any form, for example in the form of powders, granules or the like, or in other forms.

The alkali metal silicate can have a SiO ₂ / M ₂ O molar ratio of about 1.6 to 4, preferably about 1.8 to 3.5.

According to a preferred embodiment of the present invention, the builder is an alkali metal (particularly sodium or potassium).
It consists of an aqueous solution containing about 10 to 60% by weight, preferably about 35 to 50% by weight, solids content of the silicate.

The concentrated alkali metal silicate solution used in the builder is preferably obtained by solubilizing the "soluble glass" in an autoclave under pressure at 140 ° C. and optionally diluting it. It can also be obtained by other known means, such as direct digestion of sand using a concentrated solution of caustic soda.

According to NMR analysis, SiO ₂ / Na ₂ O
A solution having a 45% solids content of vitreous silicate with a molar ratio of 2 is 34% Q ₃ species, 51% Q ₂ species, 12% Q
Containing ₁ and 3% Q ₀ species, and molar ratio =
A solution with a 35% solids content of 3.5 gives 46% Q ₃
Seeds, 27% Q ₂ 'or, 16% of Q ₄ species, was found to contain _one and two percent of Q ₀ or 9% Q.

By water "bound" to the silicate is meant water in an aqueous solution not bound to inorganic compounds, in particular not in the form of crystalline hydrates.

The water / silicate weight ratio, which, expressed on a dry basis, remains bound to the silicate (which must be greater than 33/100, preferably 36/100) is such that the silicate is in polyanionic form. Indicates the need to be present. Fixing the upper limit of this ratio is within the skill of those in the art. Of course, this upper limit corresponds to the limit for keeping the silicate in a finely divided, dry form, ie in a form that can be used in detergents. For example, the water / silicate weight ratio as bound to silicate, expressed on a dry basis, is about 120/1.
Must be less than or equal to 00.

The high silicate content in the products according to the invention makes it possible to obtain very satisfactory antifouling performance, in particular in linen products or in washing machine parts.

When present in unstructured form, especially in solution, the builder sprays the washing powder on the "bottom" in the case of spraying plants or on the mixture of the components of the washing formulation in the case of dry mixtures. Can be used as a post-additive. This is within the adsorptive limits of the powder present. The resulting finely powdered mixture, if necessary, is suitably dried so that the weight ratio of water / silicate, still bound to the silicate, on a dry basis, remains above 33/100, preferably above 36/100. be able to.

The amount of silicate solution in the builder in this solution which can be used is preferably 1/100 to 3
0/100, more preferably about 10/100 to 20/10
It corresponds to a dry silicate / wash powder weight ratio of 0.

When the builder of the present invention takes a molded form, the builder of the present invention is particularly preferably about 1.6 to 4 and more preferably about 1.8 to 4.
A concentrated aqueous solution (1) of an alkali metal silicate having about 3.5 SiO ₂ / M ₂ O, and a dissolved inorganic compound which is inert to the silicate and miscible in the aqueous solution (1) ( 2) which is 5 to 55 of the total weight on a dry basis
% Of an aqueous solution (A) comprising a mixture with the inorganic compound (2) occupying less than 10% by weight of the compound (B) having the same composition as the aqueous solution (A).
The weight ratio of water / total silicate, which remains bound to total silicate on a dry basis, is 33
/ 100, preferably 36/100 or more. The symbol "M" in this specification represents an alkali metal unless otherwise specified.

The aqueous solution (A) can be produced by any means known per se. In particular, it can be prepared by introducing the inorganic compound in powder or liquid form into an aqueous silicate solution.

The expression "compound (B) having the same composition as the aqueous solution (A)" is defined as containing the alkali metal silicate and the inorganic compound as described above, and the inorganic compound being expressed on a dry basis of 5% of the total weight. Represents any compound that accounts for less than ~ 55%. This compound (B) has a water / silicate weight ratio of 33 /
100, preferably 36/100 or more.

This compound (B) can be produced by a method known per se. Thus, this can be obtained in particular by drying the same solution as the aqueous solution (A). The drying is carried out at a desired ratio of water bound to the silicate, i.e. a water / silicate weight ratio of 33/100, preferably 3/100, still bound to the silicate, on a dry basis.
It is preferable to control so as to maintain the ratio at 6/100 or more.

In the aqueous solution (A), the alkali metal silicate of the concentrated aqueous solution has a water / silicate weight ratio of 33/100, preferably 36/100 or more, which is still bonded to the silicate on a dry basis. Preferably.

The contacting operation may be carried out by addition, particularly in a known high shear mixer of the Lodige type or in a granulating means (drum, dish, etc.) at about 20 to 95 ° C., preferably 70 to 95 ° C.
It can be carried out by spraying (A) onto (B) at a temperature of about 95 ° C. The inorganic compounds which can be used are those described above.

The amount and concentration of the aqueous solution (A) to be used depends on the potential of the solution (A) and the compound (A), especially in the case of an inorganic compound forming a crystallizable hydrate. It is a function of the absorption and / or adsorption of the inorganic compounds present in the solution (A) and the compound (B) compared to the silicates present in B). The content of silicate-free water, which may be in the form of a hydrate on the support, can be determined in a known manner by differential thermal analysis or by quantitative X-ray diffraction. Water that can bind to the support in a form other than a hydrate can be obtained by any suitable physicochemical method (thermoporometry, thermogravimetric analysis, proton NMR,
IR).

The absorption and / or absorption limits of the inorganic compounds can be determined by known methods, for example by measuring the variation of the response angle at the bottom of the slip bank as a function of the amount of silicate solution added. .

If necessary, after this contacting of (A) and (B), a drying step can be carried out, but this is suitable for obtaining the desired proportion of water combined with the silicate. It is performed in a simple manner.

Particularly effective are alkali metal silicate solutions which are present in an adsorbed and / or absorbed form in the alkali metal carbonate and which take the form of cogranules of alkali metal silicate hydrate and alkali metal carbonate. A builder of the invention.

The co-granules of the alkali metal silicate hydrate and the alkali metal carbonate are prepared in the following step: (a) about 1.6 to 4, preferably about 1.8 to 3.5 SiO ₂ / M ₂ Spraying an aqueous solution consisting of a mixture of an aqueous solution of an alkali metal silicate having an O molar ratio and an alkali metal carbonate (the carbonate occupies less than 5 to 55% of the total weight on a dry basis) Spraying a rolling bed of particles having the same composition as and advancing in a rotary granulator,
In this case, the advancing speed of the particles, the thickness of the tumbling bed and the flow rate of the sprayed solution are such that each particle is converted into a plastic co-granulate while contacting each other, and (b) step (a) Optionally) drying the granules obtained in step (a), wherein these steps have a final water / silicate weight ratio of 33/10, still bound to the silicate, expressed on a dry basis.
0, preferably 36/100 or more. These cogranulates can be used as a simple and effective means for introducing silicates and carbonates into detergent compositions.

The expression "particles having the same composition as the mixture to be sprayed" means particles comprising alkali metal silicates and, on a dry basis, from 5 to 55% of the total weight of the alkali metal carbonate. . These particles preferably have a water / silicate weight ratio of 33/100, preferably 36/100 or more, still bound to the silicate, expressed on a dry basis. These particles can be produced by a method known per se. These can be obtained in particular by drying the same solution as the aqueous solution consisting of alkali metal silicates and carbonates as described above. This drying maintains the desired proportion of water bound to the silicate, i.e., the weight ratio of water / silicate still bound to the silicate, expressed on a dry basis, is 33/100, preferably 36/100 or more. Preferably, it is controlled so that

Also, the rolling bed of particles having the same composition as the mixture to be sprayed starts with a dry carbonate / silicate mixture having the same carbonate / silicate ratio as the sprayed mixture, expressed on a dry basis. And maintaining the bed until it is completely fresh with the obtained (recirculated) cogranulate.

The concentrated aqueous alkali metal silicate in an aqueous solution comprising a silicate / carbonate mixture has a water / silicate weight ratio of 33/1, expressed on a dry basis, which remains bound to the silicate.
00, preferably 36/100 or more.
The alkali metal silicates and carbonates preferably include those of sodium and potassium, especially sodium.

Between step (a) and step (b),
The co-granulate obtained in step (a) is preferably subjected to a densification operation.

According to a preferred embodiment of the present invention, the silicate solution used for producing the cogranulate has a silicate solids content of the order of 10 to 60%, preferably of the order of 35 to 50%. The spraying of the aqueous solution based on a silicate / carbonate mixture is carried out at a temperature of about 20 to 95C, preferably about 70 to 95C. This is due to the simultaneous introduction of air under pressure at the same temperature (eg by a twin-screw nozzle)
Can be promoted by The carbonate used is
It can be of normal grade. Preferably, carbonates which are readily soluble and have a high adsorptivity and / or absorption are used.

In addition to these carbonate / silicate mixture particles, small amounts (less than 10% by weight of the cogranulate) of other particles having a similar diameter and density to the carbonate / silicate mixture particles, For example, a polymer for preventing redeposition (such as carboxymethyl cellulose), an enzyme, and a polyacrylate commonly used in the detergent field may be present.

The equipment used to carry out the co-granulation operation by spraying can be a rotating dish, a pelletizer, a rotating drum, a mixer granulator or any rotary type of similar type.

A first preferred method of producing these cogranulates comprises using a rotary granulator that allows the particles to advance as a thin layer. Pelletizers having an axis of rotation inclined with respect to the horizontal at an angle of greater than 20 degrees and preferably greater than 40 degrees are particularly suitable. These shapes can vary considerably and can be, for example, truncated cones, flats, stars, combinations of these three forms, and the like.

A second preferred method of producing these cogranulates comprises using a rotating drum having a tilt angle of at least 3%, preferably at least 5%. Particles based on carbonate / silicate mixtures have a temperature of 15-200 ° C.
It advances at a temperature of preferably about 15 to 120 ° C, especially about 15 to 30 ° C. The amount of the solution based on the silicate / carbonate mixture to be sprayed and the particles based on the silicate / carbonate mixture to be used is 0.05 to 0.8 l, expressed as the sodium salt. / Kg, preferably 0.1 to 0.5 l / kg, especially 0.15 to 0.3 l / kg
It corresponds to a liquid flow rate / particle flow rate ratio (wet ratio) that can be varied within the range of kg.

The flow rate of the solution to be sprayed, the advancing speed of the particles and the thickness of the layer of advancing particles are determined by the agglomerate along with the other particles each particle absorbs the liquid and contacts in order to obtain a plastic particulate instead of a paste. It is enough to become. The advancing speed of the particles and the thickness of the layer are controlled by the speed of introduction of the particles into the granulator and by its characteristics. The residence time of the particles in a dish or drum type device is generally on the order of 15 to 40 minutes.

It is within the skill of the artisan to adapt the characteristics of the equipment used as a function of the given starting materials to the desired product. That is, in the case of a pelletizer:-its shape (frustoconical, flat, star-shaped or a combination of these three forms);-its dimensions (depth, diameter);-its tilt angle; Velocity-the relative position of the solid and liquid supply. In the case of a drum, this is: its shape (tube diameter), its tilt angle, its rotational speed, its tube loading, its relative position of the solid and liquid supply.

The densification operation can be carried out at room temperature by rolling the cogranulate obtained in step (a), ie, the granulation step, with a rotary device. This device may be stand-alone or may be dependent on a granulation device. This densification process
This can be done advantageously by introducing the cogranulate into a rotating drum and allowing it to stay. The tilt angle of the rotating drum is at least 3%, preferably at least 5%. The dimensions of the drum, its rotational speed and the residence time of the cogranulate are a function of the required density. The stay time is generally about 20 minutes to 3 hours, preferably about 20 to 90 minutes. A mixer-type granulator is also suitable for this densification operation.

Thus, the co-granulation and densification operations can be carried out in the same apparatus, for example in a star-shaped pelletizer, and the densification of the co-granulate tumbles the co-granulate in the last step of the apparatus. Achieved by:
Similarly, these two operations can be performed on a drum having two zones.

Thus, the cogranulate, which is optionally densified, can be dried by any known means. A particularly effective method is in the fluidized bed with the aid of the flow of air, of the order of 40-90 ° C, preferably 60-80 ° C.
Drying at about the same temperature. This operation is carried out for a period of time which is a function of the air temperature, the water content of the co-granulate as it leaves the granulator, the desired water content of the dried co-granulate and the fluidization conditions. Those skilled in the art will know how to adapt these various conditions to the required products.

The co-granules based on sodium silicate hydrate and sodium carbonate which can be obtained according to the process according to the invention and which are particularly suitable for the preparation of detergent compositions for washing machines and dishwashers are: 1. Adsorbed and / or absorbed by alkali metal carbonate
Alkali metal (especially sodium or potassium) silicates having a SiO ₂ / M ₂ O molar ratio of the order of 6 to 4 (the carbonates being 5 to 55% of the weight of the silicates adsorbed and / or absorbed by said carbonates) Less than 30%), wherein the weight ratio of water / silicate still bound to the silicate, on a dry basis, is 33/100, preferably 36/100 or more; -0.4 to 1.5 g / cm ³ , preferably 0.5 to
1.5 g / cm ³ or so, especially 0.75~1g / cm ³ order of bulk density, the -log ₁₀ (standard deviation) of 0.02 to 0.5 preferably in the case of 0.05 to 0.3 0 It has a median particle diameter (within the meaning of the percentage of cumulative passage) of about 0.4 to 1.8 mm, preferably about 0.5 to 0.8 mm.

The weight ratio of water / silicate, still bound to silicate, expressed on a dry basis, is preferably about 120/10
Must be less than or equal to 0.

The above process, which includes a co-granulation step and optionally a densification and drying step, provides a co-granulate based on alkali metal silicate hydrate and alkali metal carbonate and which rapidly dissolves in water. Make it possible.

Thus, the rate of 90% and 95% dissolution of the cogranulate in water according to the invention is less than 3 minutes and less than 5 minutes, respectively. The rate of 90% or 95% dissolution in water is defined as 90% or 95% of the product in water at 20 ° C.
Means the time required to dissolve at a concentration of 5 g / l.

When shaped (powder, cogranulate, etc.), the builder of the present invention is used in detergent compositions for dishwashers in a proportion of 3 to 90% by weight, preferably 3 to 70% by weight of the composition. Used in. The amount used in the composition for a washing machine is about 3 to 60% by weight of the composition, preferably 3 to 4%.
On the order of 0% (these amounts are expressed as dry silicate weight based on the weight of the composition).

In addition to the builder constituting the object of the present invention,
At least one surfactant is present in the cleaning composition in an amount which may be in the range of 8-20% by weight of the composition and preferably in an amount of the order of 10-15%.

Examples of these surfactants include: alkali metal soaps (alkali metal salts of C ₈ -C ₂₄ fatty acids), alkali metal sulfonates (C ₈ -C ₁₃ alkylbenzene sulfonates, C ₁₂ -C 2 ₁₆ alkyl alkylsulfonate), oxyethylenated and sulfated C ₆ -C
₁₆ fatty alcohols, oxyethylenated and sulfated C ₈ ~
C ₁₃ alkylphenol, anionic surface active agents such as alkali metal sulfosuccinic acid salts (C ₁₂ -C ₁₆ alkyl sulfosuccinic acid salt), - polyoxyethylenated C ₆ -C ₁₂ alkylphenols, oxyethylenated C ₈ -C ₂₂ Non-ionic surfactants such as aliphatic alcohols, ethylene oxide-propylene oxide block copolymers and optionally polyoxyethylenated carboxylic acid amides, amphoteric surfactants of the alkyldimethyl betaine type, alkyltrimethylammonium or alkyldimethylethyl There may be mentioned cationic surfactants of the ammonium chloride or bromide type.

Various components can additionally be present in the detergent composition, examples of which include, in builders:-a proportion of phosphate less than 25% of the total weight of the formulation; Zeolite up to about 40% of the total weight of the formulation; sodium carbonate up to about 80% of the total weight of the formulation; nitriloacetic acid up to about 10% of the total weight of the formulation; Up to about 50% citric acid, tartaric acid can be mentioned, and the total amount of builder is about 0.2-80%, preferably 20-4% of the total weight of the detergent composition.
Equivalent to 5%. Examples also include:-up to about 30% of the total weight of the detergent composition of perborate, percarbonate, chloroisocyanurate and N, N, N ',
A bleach of the N'-tetraacetylethylenediamine (TAED) type; an antiredeposition agent of the carboxymethylcellulose or methylcellulose type in an amount which can be up to about 5% of the total weight of the detergent composition; An anti-fouling agent of the acrylic acid-maleic anhydride copolymer type, which may be in the range of up to about 5% of the total weight of the composition;-in the range of up to about 50% of the total weight of the detergent composition. Sodium sulphate-type fillers for detergent powders in amounts which may be included.

[0060]

The following examples illustrate the invention but do not limit the scope of the invention.

[0061] Example 1 builder compound synthesized was used in this synthesis of: - sodium silicate: solution SiO ₂ / Na ₂ O molar ratio = 2.8 having the following characteristics, solids content: 45
% By weight, relative density: 1.500, distribution of polyanion species (mol% of silicon): Q ₀ = 0.8%, Q ₁ = 6.2
%, Q ₂ and Q ₃ = 83%, Q ₄ = 10%-Sodium carbonate: anhydrous powder having the following physical properties Bulk density: 1.1 g / cm ³ , Particle size: d ₅₀ = 0.5 mm Synthesis: pre-dissolved Sodium carbonate was added to the sodium silicate solution heated to 80 ° C. with stirring. In this case, the addition of water to the sodium carbonate made it possible to work with a mixed solution having the same solids content as the initial silicate solution. The mixing was carried out such that, on a dry basis, the sodium carbonate accounted for 30% of the total weight of the silicate and carbonate. The mixed solution was dried as a thin layer in an oven at 20 ° C. for 20 hours. The resulting solid was then ground with a "Forplex" mill. This final step consisted of drying in a fluidized bed at 30-40 ° C. to obtain a solid having the following composition: Therefore, sodium carbonate represents 3% of the total weight of silicate and carbonate on a dry basis.
It accounted for 0%. The water / silicate weight ratio as bound to the silicate was 49.7 / 100. The product has the following properties: bulk density: 0.8 g / cm ³ particle size: d ₅₀ = 0.5 mm, d ₁₀ = 0.1 mm, d ₉₀ =
1 mm-Solubility: 4 minutes or less (99%
℃ conductivity measuring method of an aqueous solution containing the product of 3 g / l in) - calcium sequestering ability: had CaCO ₃ 197 mg per anhydrous product 1g. This sequestering ability is evaluated by measuring the residual calcium concentration at time t = 15 minutes. In this case, the product to be tested is introduced at time t = 0 into a solution of known calcium concentration (solution buffered at pH 10).

Example 2 Preparation of Co-granules The compounds used were: - Sodium silicate solution: SiO ₂ / Na ₂ O molar ratio = 2.0 having the following characteristics, solids content: 4
5.5 wt%, density: 1.54 g / cm ³ -sprayed silicate: silicate having the following physical properties: SiO ₂ / Na ₂ O molar ratio = 2.05, solid content: 2
0%, density: 0.55 g / cm ³ , particle size: d ₅₀ = 0.1
2 mm-sodium carbonate: light soda having the following physical properties: density: 0.6 g / cm ³ , particle size: d ₅₀ = 0.12 mm solution containing 38% by weight of carbonate (expressed as silicate and carbonate on a dry basis) ) Was prepared at 85 ° C. This was done by incorporating the carbonate solution into the silicate solution at a ratio of two. The solid content of the mixed solution thus prepared was 37.7%. The granulation of this solution is 2
1,300 mm length and 500 diameter rotating at 0 times / minute
mm drum. Granulation was initiated from a stock bed consisting of a ground mixture of light carbonate and sprayed silicate in a ratio of 2. The carbonate and silicate composition of this mixture is:
It was that of a mixed solution. Granulation took place in the first part of the drum, where the solution was sprayed onto the powder bed via a sprinkler bar. Drying was performed in a second section of the drum equipped with a lift and purged countercurrently with hot air. Therefore, granulation, densification and drying were performed in the same equipment.
A portion of the product exiting the drum is ground and 0.2-1.
After sieving the 25 mm fraction, it was recycled to the drum head. Thus, at steady state, i.e., when the initial bed stock is completely renewed by the newly formed product, the granulation parameters are:-mixed solution feed: 6-8 l / h-powder feed (Recirculation): 50 kg / h-Wet ratio: 0.12-0.16 l / kg-Dry air flow rate: 110-120 m < ³ > / h-Dry air temperature: 105-110 [deg.] C-Average residence time in drum: 30 ４０40 minutes. The cogranulate was thus recovered, the properties of which were: a carbonate / silicate ratio of 38/62 on a dry basis, a water / carbonate bound to silicate on a dry basis =
The particle size in the case where ₅₁ / ₁₀₀ -bulk density = 0.89 g / cm ³ -log ₁₀ (standard deviation) was 0.37: d ₅₀ = 0.45 mm and d ₉₅ = 0.8 mm. The granules obtained have the following dissolution time: 90% by weight of the product dissolve in 50 s (3 at 20 ° C.)
95% by weight of the product dissolves in 67 s (3 at 20 ° C.)
Aqueous solution containing 5 g / l)-showed that 99% by weight of the product dissolved in 154 s (aqueous solution containing 35 g / l at 20 ° C).

As a comparison, a simple dry initial mixture of carbonate and spray silicate, which initially forms the bed stock (which does not constitute an object of the invention), has the following dissolution time: 90% by weight of product % Dissolves in 55 s (3 at 20 ° C.)
95% by weight of the product dissolves in 108 s (aqueous solution containing 35 g / l at 20 ° C.) 99% by weight of the product dissolves in 266 s (35 g / l at 20 ° C.) aqueous solution containing 1). Calcium sequestering ability was CaCO ₃ 243~249mg per 1g anhydrous product. The sequestering ability was evaluated as in Example 1.

Example 3 Production of Co-granulates The granulation process is the same as in Example 2, but the granulator is operated in an open loop, ie it comprises a dry carbonate / sprayed silicate mixture and a mixed solution. Was fed but no recycle of the product obtained was carried out. Also, drying was simultaneous. Granulation parameters, - mixing a solution supply rate: 6-8 l / h - Powder supply rate: 30kg / h - wet ratio: from 0.2 to .27 l / kg - Drying air flow: 110~120m ³ / h -Dry air temperature: 105-110 [deg.] C-Average residence time on the drum: 30-40 minutes. The cogranulate was thus recovered, the properties being: a carbonate / silicate ratio of 37/63 on a dry basis; a water / carbonate bound to silicate on a dry basis =
The particle size in the case where 51 / ₁₀₀ -bulk density = 0.54 g / cm ³ -log ₁₀ (standard deviation) was 0.12: d ₅₀ = 0.57 mm, d ₉₅ = 0.78 mm. The granulate obtained has the following dissolution time: 90% by weight of the product dissolves in 55 s (3% at 20 ° C.)
95% by weight of the product dissolves in 122 s (aqueous solution with a concentration of 35 g / l at 20 ° C.) 99% by weight of the product dissolves in 300 s (35 g / l at 20 ° C.) 1 aqueous solution). The calcium sequestering ability was 245 mg CaCO _{3 /} g anhydrous product. The sequestering ability was evaluated as in Example 1.

These cogranulates were introduced by dry mixing together with the additives to give the following compositions for washing machines. Detergent composition parts by weight-Granules obtained 40-Trade name "Sokalan CP5" 4.8 (copolymer of BASF)-Trade name "Tixolex 25" 5 (Amorphous silicoaluminate from Rhone Poulin) -Sodium sulfate 7-Trade name "TAED" 5-Trade name "LAB (80%)" 6-Trade name "Synperonic A3" 3-Trade name "Synperonic A9" 9-Trade name "Esperase" 0.3 (Novo -Brand name "Tinopal DMSX" 0.2-Brand name "Tinopal SOP" 0.2 (whitening agent from Ciba-Geigy)-Antifoam 2.5-Carboxymethylcellulose 2

The performance test for dirt removal was conducted in Wascat.
or FOR 71 "type washing machines. The test conditions were as follows:-Cycles used: 60 ° C-Total cycle time: 70 minutes, no pre-wash-Number of cycles: 3 per wash-Water Hardness: 32 French hardness-Wash load: 3.5 kg piece of white cotton cloth-Cloth tested: The following two sets of cloths were pinned on the above piece of cloth and introduced into the wash:

Method for Measuring Stain Removal By photometry (measurement of the amount of light reflected by the cloth), it is possible to calculate the percentage of stain removal.
A "Datacalor Elrepho 2000" instrument is used. The removal of dirt is calculated by the formula:% removal = (CB) / (AB) × 100 [where A = reflectance of control white sample, B = reflectance of control contamination sample, C = washing Reflectance of later contaminated sample]. The reflectance is measured with the aid of the blue component without the action of an optical brightener. Number of measurements performed per sample = 4 Number of samples per wash = 2 Number of washes = 3 That is, 4 × 2 × 3 = 24 measurements per stain, product and concentration.

The anti-fouling substance forming performance test in a washing machine is as follows.
It was performed on a "Schultess Super 6 De Luxer" drum machine.
The test conditions were:-Cycle used: 60 ° C-Total cycle time: 65 minutes, no pre-wash-Number of cycles: 25 cumulative washes-Water hardness: 21.2 French hardness-Test cloth used: NFT standard 73 A control strip exactly corresponding to the standard described in .600-Wash load: 3 kg of 100% cotton thick towel-Detergent usage: 5 g / l. The test pieces that had undergone 25 washes were dried. It was weighed and calcined at 900 ° C. The weight percent ash was measured relative to the initial weight of the specimen. The results of each test are listed in Table I.

Comparative Example 4 Production of Cogranulate The granulator system consisted of the same drum rotating at 40 revolutions / minute as described in Example 2. The diaphragm at the outlet was adjusted so that the residence time of the particles was about 15 to 20 minutes.
The drum was continuously fed with carbonate powder having the same properties as the powder of Example 2 at a rate of 37 kg / h. On this powder, the same 80 ° C. silicate solution as in Example 2 using a two-part flat jet nozzle located one-third of the length of the drum and rotated in the drum At a flow rate of 18 l / h with the help of air at 80 ° C. The co-granulate leaving the drum was at room temperature and had a density of 0.68 g / cm ³ . Then 50
Having a diameter of 0 mm and a length of 1,300 mm and 5%
The cogranular body was discontinuously densified for 1 hour on a rotating drum having a smooth wall with an inclination of. The rotation speed of the drum is 20
Times / minute. The granules thus obtained were dried in a fluidized bed at a temperature of about 65 ° C. (fluidized air temperature of 70 ° C.) for 15 minutes. The dried product has the following properties: a carbonate / silicate ratio of 66/34 on a dry basis, a water / carbonate ratio of silicate bound on a dry basis =
61/100 - calcium sequestering ability: had CaCO ₃ 245 mg per anhydrous product 1g. The sequestering ability was evaluated as in Example 1. The granules had excellent behavior during storage. These co-granules were dry blended with the additives to give a washing machine composition similar to that described in Example 4 (excluding the co-granules). In addition, a performance test for removing dirt and deposits was performed on the laundry composition.
The results are described in Table I.

[0070]

[Table 1]

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Pascal Take, Bille-sous-Saint-Loup, France, Rue de Primvale, 7 (56) References JP-A-4-275400 (JP, A)

Claims (13)

(57) [Claims] (A) SiO ₂ / M _{2 of} about 1.6 to ₄
A mixture of an aqueous solution of an alkali metal silicate having an O molar ratio (where M represents an alkali metal) and an alkali metal carbonate, wherein the carbonate represents less than 5 to 55% of the total weight on a dry basis. Is sprayed onto a rolling bed of particles having the same composition as the mixture to be sprayed and advancing in a rotary granulator, wherein the advancing speed of the particles, the thickness of the rolling bed and The flow rate of the sprayed solution is such that each particle is converted into a plastic cogranulate while in contact with each other, and (b) optionally drying the granulate obtained in step (a). Alkali metal silicates, characterized in that they are carried out in such a way that the final weight ratio of water / silicate, still bound to silicate, on a dry basis, is greater than 33/100. Salt hydrate and alka Preparation of co-granules with the metal carbonate. 2. The method according to claim 1, wherein the alkali metal silicate and the alkali metal carbonate are sodium or potassium. 3. The method according to claim 1, wherein between the step (a) and the step (b), the cogranulate obtained in the step (a) is subjected to a densification operation. 4. An aqueous solution of a silicate having a silicate solids content of about 10 to 60%.
A method according to any one of the preceding claims. 5. The method according to claim 1, wherein step (a) is carried out at a temperature on the order of 20 to 95 ° C. 6. The particle according to claim 1, wherein the particles having the same composition as the mixture to be sprayed are obtained by drying the same solution as an aqueous solution comprising an alkali metal silicate and a carbonate. The method described in the section. 7. The method according to claim 1, wherein the granulator is a rotary granulator for advancing particles in a thin layer. 8. The method according to claim 6, wherein the rotary granulator is a pelletizer. 9. The method according to claim 1, wherein the rotary granulator is a drum. 10. The process according to claim 1, wherein the particles having the same composition as the mixture to be sprayed advance at a temperature of the order of 15 to 200 ° C. 11. A solution based on a silicate / carbonate mixture to be sprayed and a silicate /
Characterized in that the amount of particles based on the carbonate mixture corresponds to a liquid flow / particle flow ratio which, when expressed as the sodium salt, can vary within the range of 0.05 to 0.8 l / kg. The method according to any one of claims 1 to 10. 12. The method according to claim 1, wherein the densification operation is carried out at room temperature by rolling the cogranulate obtained in step (a) with a rotary device. The method described in the section. 13. Spheroidal cogranulates based on hydrated alkali metal silicates and alkali metal carbonates, which are adsorbed and / or absorbed on alkali metal carbonates.
Alkali metal silicates having a SiO ₂ / M ₂ O molar ratio of about 6-4 (the carbonate accounts for less than 5-55% of the weight of the adsorption and / or absorbed silicate by salt carbonate acid)
Wherein the weight ratio of water / silicate still bound to the silicate, expressed on a dry basis, is 33/100 or more; bulk density of about -0.4 to 1.5 g / cm ³ ; ₁₀ A spherical cogranular material having a median particle size of about 0.4 to 1.8 mm when (standard deviation) is 0.02 to 0.5.