SK19793A3 - A builder based on silicate and on an inorganic product - 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

The invention relates to a builder consisting of a solution of alkali metal silicates rich in silicon atoms in the form of Q ₂ ^and wherein the solution is in the presence of an inorganic product which is inert to said silicates. This builder is intended for detergent compositions, in particular for washing powders, especially for washing machines and dishwashers.

The invention also relates to mixed granules of alkali metal silicate hydrates and alkali metal carbonates.

Said builder must have a property known as a softening effect on the water used for washing. It must therefore remove calcium and magnesium, which are present in water in the form of soluble salts and, in laundry soils, in more or less soluble complex forms. The removal of calcium and magnesium must be carried out by complexing in the form of soluble substances or by ion exchange or precipitation. Where precipitation is used, such precipitation must be carried out in a controlled manner in order to avoid increments in the laundry or on the washing machine components.

This controlled precipitation is achieved in particular by the use of water-soluble polymers that exhibit affinity for calcium and magnesium.

The builder must also promote the emulsifying effect of the surfactants on the greasy soil and the dispersing effect on the pigment soils, such as metal oxides, clays, silicas, various dusts, humus, limestone and soot.

This dispersing effect is generally achieved due to the presence of polyanions contributing to the high density of negative charges at the phase interface.

The builder must also enhance the ionic strength, which activates the effectiveness of the surfactants, especially by increasing the micelle size.

The builder must also provide 0H ~ ions for saponification of fats and also in order to increase the negative surface charge on the textile surface and on the dirt particles.

BACKGROUND OF THE INVENTION

Silicates have long been used as good detergent ingredients, although they are usually less used in phosphate-free detergent compositions.

The most widely used silicates in the present invention are silicates having a SiCl 2 / Na 2 O molar ratio between 1.6 and 2.7.

These silicates are commercially available in the form of concentrated solutions having a dry matter content of about 35 to 45% by weight or in the form of spray-dried and optionally compacted silicate powders.

Concentrated commercial solutions are in most cases prepared from the so-called glassy completely amorphous silicates, which are also known as soluble glasses.

These soluble glasses are hydrosolubilized in an autoclave at a pressure of 140 ° C. Commercial solutions are obtained which have a dry matter content of about 45% by weight in the case of a silicate with the indicated ratio of 2 and about 35% in the case of a silicate with the said ratio of 3.5. ·

These concentrated silicate solutions are introduced into the aqueous drying slurry containing the other components of the washing powder by means of a laundry detergent formulator. The suspension is then dried in a spray drier. The spray dried together with the other ingredients] contains only about 25% of the accompanying water; na ‘.-so !; its dry matter, or even less.

As for the commercial silicate powder, it is obtained by spray-drying concentrated solutions of glassy silicates; in order to maintain the good solubility of this product, 19 to 22% by weight of water, based on the weight of the final product, must be retained in the powder.

SUMMARY OF THE INVENTION

It has now been found that if this silicate powder, which contains only 19 to 22% by weight of accompanying water (based on the weight of the final product), dissolves in the washing bath in an amount of 1 to 3 g / liter, then it has only weak builder properties.

In fact, this dissolved silicate powder leads predominantly to the formation of monomeric silicon compounds of the general formula Si (OX), in which X represents a hydrogen atom or a sodium atom, which do not have a builder effect. Such monomeric substances can only be combined to form polyanions if the silicate concentration is at least 50 to 500 g / liter, and does so slowly.

Such concentrations and slow kinetics of polymerization of said monomer substances are not compatible with washing conditions and washing times.

Of course, what has been found in the case of a powder containing 19 to 22% chemically accompanying water (based on the weight of the final product) also applies to formulations containing a silicate containing approximately 25% accompanying water (based on the silicate dry matter) which are prepared by introducing concentrated the silicate solution into an aqueous suspension containing the other ingredients of the washing powder and drying.

It has now been found that if the alkali metal silicate in solution is rich in silicon atoms in Q ₉ and Q forms, these substances, which are present in the form of polyanions in the case, are diluted in a washing medium to a concentration? / l, a sufficiently long lifetime to enable them to act as a builder in the composition.

The term " silicon atoms " ^and " Q3 " represent the degree of mutual association of silicon atoms; Q ₉ number, z? each silicon atom participates in two bonds -Si-O-h1-, the remaining two bonds being the bonding ends of -Si-OX, wherein X represents an alkali metal atom or a hydrogen atom; Q ^ means that each silicon atom participates in the three -Si-O-Si- bonds, the remaining bond being the -Si-OX bonding end.

The builder for the detergent composition according to the invention consists of an aqueous solution of an alkali metal silicate, in particular sodium or potassium silicate, with a SiOg / MgO molar ratio of about 1.6 to 4, and an inorganic product which is inert to said silicate and miscible with said silicate solution, wherein the product represents 5 to less than 55% of the total weight, expressed as dry matter, and the weight ratio of residual accompanying water in silicate to silicate, expressed as dry matter, is greater than or equal to 33: 100, preferably 36 : 100, wherein M is an alkali metal.

The term inert means chemically inert.

The organic products which are inert to the silicate and miscible with the aqueous silicate solution are preferably water-soluble. Examples of such products are: sodium carbonate, sodium sulfate, sodium borate, sodium perborate, sodium metasilicate, phosphates or polyphosphates such as sodium phosphate or sodium tripolyphosphate, etc., which are used singly or in admixture with each other.

Preferably, detergent-active products, and in particular sodium carbonate, are used.

Said inorganic product constitutes 5 to less than 55%, preferably 20 to 40%, of the total weight, expressed as dry matter, i. the sum of the weight of the solution, expressed as dry matter, and the weight of the inorganic product.

Said inorganic product is either introduced into an aqueous solution of an alkali metal silicate or is introduced. and then mixed with said aqueous alkali metal silicate solution.

The builder of the invention may be in any form, either in a structured form (e.g. powder or granulate) or in another form.

Said silicate may have a SiO 2 / Al 2 O molar ratio of about 1.6 to 4, preferably about 1.8 to 3.5.

According to a preferred embodiment of the invention said builder is formed by an aqueous solution containing about 10 to 60%, preferably 35 to 50% by weight of the dry matter of alkali metal silicate, in particular sodium or potassium silicate.

The concentrated alkali metal silicate solution used in the builder is preferably obtained by hydrosolubilizing the soluble glasses in an autoclave under pressure at 140 ° C and optionally subsequent dilution; this solution can also be obtained by other known methods, for example, by direct digestion of the sand using caustic soda in a concentrated solution.

Nuclear magnetic resonance spectroscopic analysis revealed that:

- a solution of 45% dry matter content of silicate glass having a molar ratio SiC ^ / Na ^ = 2 contains 34% of the mold forms 51% of Q _2, 12% and 3% of the mold form φθ;

- a solution of 35% dry matter content of silicate glass having a molar ratio SiO ₂ / Na ₂ O equal to 3 * 5 containing 46% of Form

Q? 27% Q ₂ form, 16% form, 9% of the form Q _(a 2% Form Q _Q.

The silicate accompanying water is water in said aqueous solution which is not combined with the inorganic product, in particular not in crystalline hydrate form.

The weight ratio of residual accompanying water of silicate to silicate, expressed as dry matter, which must be greater than or equal to 33: 100, preferably 36: 100, corresponds to the need to be in the presence of silicates in polyanionic forms. level of the corresponding limits of course, in the silicate torých maintain a free flowing powder / free-f i ^(; νη ny / f Ormuz, i.e., the form usable in the detergentnýcn kompozľc.i For simple presentation, the weight ratio of residue "." ester companion water of silicate to silicate, expressed as dry matter, must be less than or equal to 120: 100.

In particular, the higher silicate content of the products according to the invention makes it possible to obtain a very satisfactory anti-incrustation effect on the laundry or on the washing machine components.

If present in the non-structural form and in particular in solution, the builder may be used as an additional ingredient added by spraying the scouring powder onto the tower when the scouring powder is dried from the solution in a spray drier or by spraying a mixture of scouring formulation ingredients; wherein said laundry formulation is obtained by dry blending the components, said spraying being carried out to the extent that it is within the absorbent capacity of the powders. The obtained powder mixture may be dried under mild conditions if necessary so that the weight ratio of residual silicate to silicate accompanying water, expressed as dry matter, remains greater than or equal to 33: 100, preferably 36: 100.

The amount of silicate solution in this builder in the solution that can be used preferably corresponds to a weight ratio of dry silicate to washing powder of between 1: 100 and 30: 100, and more preferably a ratio of about 10: 100 to 20: 100.

When present in a structural form, the builder of the invention may be particularly prepared by introducing an aqueous solution A consisting of a mixture of a concentrated aqueous solution of alkali metal silicate 1 with a SiO2 / M2O molar ratio of about 1.6 to 4, preferably about 1.8 to 3, 5, and from the dissolved inorganic product 2, said inorganic product being inert to said silicate and miscible with aqueous solution 1 and representing 5 to less than 55% of the total weight, expressed as dry matter, of the mixture B 'of the composition which is identical to the aforesaid aqueous solution A, and so on, the weight ratio of the residual accompanying water of the total silicate content to the total silicate content, expressed as. eye dry matter, after this contact was greater than or equal to 33: 100, especially 36: 100.

Unless otherwise indicated, M is an alkali metal in the foregoing and following.

Said solution A may be prepared by any known method. In particular, it can be prepared by introducing the inorganic product in powder or liquid form into an aqueous silicate solution.

Mixture B of a composition identical to aqueous solution A is any mixture comprising the above alkali metal silicate and an inorganic product, wherein the inorganic product represents 5 to less than 55% of the total weight, expressed as dry matter. This mixture B preferably has a weight ratio of residual accompanying water of silicate to silicate, expressed as dry matter, greater than or equal to 33: 100, preferably 36: 100.

This mixture B can be obtained by any known method. In particular, it can be obtained by drying a solution identical to aqueous solution A. This drying is preferably controlled to maintain the desired amount of silicate accompanying water, i. wherein the weight ratio of residual silicate to silicate accompanying water, expressed as dry matter, is greater than or equal to 33: 100, preferably 36: 100.

In aqueous solution A, the concentrated aqueous solution of alkali metal silicate preferably has a weight ratio of residual accompanying water of silicate to silicate, expressed as dry matter, greater than or equal to 33: 100, preferably 36: 100.

Said contacting may be accomplished by adding, in particular by spraying component A to component B, in any known high shear mixer, in particular in a Lodige-type or granulating device (e.g., drum or disc type), at a temperature of about 20 to 95 °. C, preferably at a temperature of about 70 to 95 ° C.

usable inorganic products have b ^<: u? hi thin above.

The amounts and concentrations of aqueous solution A to be used are a function of the absorption and / or adsorption capacity of the inorganic products present in solution z'i and mixture B relative to the silicate present in solution Λ and mixture B, taking into account the potential formation potential. especially crystallizable hydrates for said inorganic products; the content of silicate water, which may be in the form of a hydrate in the carrier, can be determined in a known manner by differential thermal analysis or by quantitative X-ray diffraction. Water, which may be combined with a carrier in a form other than a hydrate form, may be determined by appropriate physico-chemical methods (thermoporosimetry, thermogravimetry, proton nuclear magnetic resonance spectroscopy, and infrared spectroscopy).

The limit of the absorption and / or adsorption capacity of said mineral products can be determined by known methods, for example by measuring the change in the angle of repose gripped by the slope of a small

- 9 amounts of poured material with the base of the pad, depending on the amount of silicate solution added.

Optionally, after contacting component A and component B, a drying step may be applied, the drying being carried out under mild conditions, but so as to achieve the desired amount of silicate accompanying water.

Solutions of alkali metal silicate in adsorbed and / or absorbed form on alkali metal carbonate having the form of mixed granules of alkali metal silicate hydrate and alkali metal carbonate are builders according to the invention which are particularly effective.

The essence of said mixed granules of alkali metal silicate hydrates and alkali metal carbonates is that they can be obtained by a process comprising the following steps:

a) atomizing an aqueous solution consisting of an aqueous solution of an alkali metal silicate having a SiO 2 / MgO ratio of about 1.6 to 4, preferably about 1.8 to 3.9, an alkali metal carbonate, wherein the carbonate represents 5 to less than 55% of the total weight, expressed as dry matter, on a large bed of particles of the composition identical to the spray mixture passing through the rotary granulation device, the particle velocity, rolling bed thickness and spray solution flow rate selected b) optionally drying said blended granules obtained in step a /, wherein said steps are carried out such that the final weight ratio of silicate to silicate accompanying water, expressed as dry matter, was greater than or equal to 33: 100, preferably 36: 100.

These mixed granules can be used as a simple and effective means for introducing silicate and carbonate into laundry compositions.

Particles of the composition identical to the spray mixture are understood to mean particles comprising an alkali metal silicate and an alkali metal carbonate representing 5 to less than 55% of the total weight, expressed as dry matter. These particles preferably have a weight ratio of residual accompanying water of silicate to silicate, expressed as dry matter, greater than or equal to 33: 100, preferably 36: 100.

These particles can be obtained by any known method. They may be obtained in particular by drying a solution identical to the aqueous solution formed by the alkali metal silicate and alkali metal carbonate mentioned above. This drying is preferably controlled to maintain the desired amount of silicate accompanying water, i. in order to achieve a weight ratio of residual accompanying water of silicate to silicate, expressed as dry matter, of greater than or equal to 33: 100, preferably 36: 100.

The rolling bed of the particles of the composition identical to the spray mixture can also be obtained by initially removing from a dry carbonate / silicate mixture having a carbonate / silicate ratio, expressed as dry matter, identical to the spray solution, until when this bed is completely recovered by the obtained mixed granulate (recycling).

The concentrated aqueous solution of alkali metal silicate in an aqueous solution of a mixture of silicate and carbonate preferably has a weight ratio of silicate to silicate water, expressed as dry matter, greater than or equal to 33: 100, preferably 36: 100.

Among the alkali metal silicates and carbonates, sodium and potassium silicates and carbonates are preferred, with sodium silicate and sodium carbonate being particularly preferred.

Steps a / and b) may advantageously include a step in which the mixed granulate obtained in step a / is subjected to a compacting operation.

According to a preferred embodiment of the invention, the silicate solution used during the preparation of the mixed granulate has a silicate dry matter content of about 10 to 60%, preferably about 35 to 50%.

The spraying of the aqueous solution based on a mixture of silicate and carbonate is carried out at a temperature of 20 to 95 ° C, preferably at a temperature of about 70 to 95 ° C; this spraying can be aided by simultaneous introduction (for example by means of a double spraying nozzle) of compressed air of the same temperature.

The carbonates used are of conventional quality. Preference is given to using carbonates which dissolve readily and which have a high adsorption and absorption capacity.

In addition to these carbonate / silicate particles there may also be a small amount (less than 10% based on the weight of the mixed granulate / other particles such as antiredeposition polymers / carboxymethylcellulose and the like), enzymes, polyacrylates, etc., which are usually present. use the detergent compositions industry and which have a direct effect; > A density close to the diameter and particle density of the mixture of carbon / lm em hitanium.

The device used to effect the mixed spray can be any rotary device, such as a rotary bowl device, a pelletizer, a rotary drum device, a mixer-granulator, or the like.

A first preferred method of producing these blended granules is to use a rotary granulator to allow the particles to progress in a thin layer. Particularly suitable are pelletizers having an axis of rotation inclined relative to the horizontal plane at an angle of greater than 20, preferably greater than 4-0; these pelletizers may have a different geometry: frustoconical, flat, stepped, combined from the previous three geuinets, and so on.

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

The carbonate-silicate-based particles are passed through a granulating apparatus at a temperature of about 15 to 120 ° C, in particular at a temperature of about 15 to 30 ° C.

The amounts of the silicate-carbonate-based solution to be atomized and the silicate-carbonate-based particles used correspond to a liquid flow rate (particle flow rate / wetting ratio) which can range from 0.05 to 0.8 lAg, preferably from 0.1 to 0.5 L / kg and particularly preferably from 0.15 to 0.3 L / kg, these values refer to sodium salts.

The flow rate of the spray solution, the particle velocity and the layer thickness of the advancing particles are selected such that each particle absorbs liquid and agglomerates with the other particles it comes into contact to form plastic granules and not a paste.

The speed of the particles and the thickness of the particulate layer are controlled by the rate of introduction of the particles into the granulation apparatus and the characteristics of the granulation apparatus.

Particle residence time in the granulation apparatus ίί ^; Typically, the drum or drum type is about 15 to 40 past.

It is within the skill of the skilled artisan to adjust the parameters of the pelletizer according to the starting material so as to obtain the desired product, especially in the case of a pelletizer for which it is necessary to select appropriately:

- its geometry Aomo-cone, flat, stepped or a combination of the three geometries /,

- its dimensions / depth, diameter /,

- its angle of inclination,

its rotation speed, and

- the relative position of the solid and liquid feed.

In the case of a drum granulation device, the following shall be chosen as regards the drum itself:

- its geometry (diameter of cylindrical part),

- its angle of inclination,

- its rotation speed,

batch size, and

- mutual position of solid and liquid charge.

Said compacting operation can be carried out at ambient temperature by rolling the mixed granulate obtained in step a / i. in a granulation step.

The device may be dependent on the granulation device or may be independent of the granulation device.

Said compacting step may advantageously be accomplished by introducing said mixed granulate into a rotating drum and remaining therein for a certain period of time. The angle of inclination of the rotary drum is at least 3%, preferably at least 5%. The dimensions of the drum, its speed of rotation and the residence time of the mixed granulate in the drum depend on the desired density of the resulting granulate; the residence time of the granulate in the rotary drum is usually about 20 minutes to 3 hours, preferably about 20 to 90 minutes.

Suitable devices for carrying out the compaction step are mixer-granulator devices. Mixing granulation and compacting operations can be carried out in a single device, for example in a stepped / terraced / pelletized pelletizer, whereby the compaction of the mixed granulate is achieved by rolling the aforementioned. the mixed granulate in the last step of the apparatus; likewise, the two operations can be performed in a dual profile drum.

The mixed granulate, which has been optionally compacted, can be dried by any known method. A particularly efficient method of drying is fluid bed drying using a jet of air having a temperature of about 40 to 90 ° C, preferably about 60 to 80 ° C. This drying operation is carried out for a time that depends on the temperature of the air used, the water content of the the granulate after leaving the granulation apparatus, the desired water content of the dried mixed granulate and the fluidization conditions. It is within the skill of one of ordinary skill in the art to adjust said parameters to obtain the desired product.

Mixed granules based on hydrates of alkali metal silicate and sodium carbonate, which can be obtained as described above and which are particularly suitable for the preparation of detergent compositions for washing machines and dishwashers, are characterized by having:

- an alkali metal silicate, in particular sodium or potassium silicate, with a SiO2 / MgO molar ratio of about 1.6 to 4, adsorbed and / or absorbed on the alkali metal carbonate, the carbonate representing 5 to less than 55% of the total weight of the silicate adsorbed and / or absorbed by carbonate and the weight ratio of residual silicate to silicate, expressed as dry matter, is greater than or equal to 33: 100, preferably 36: 100.

an unshaked bulk density of about 0.4 to 1.5 g / cm 2, preferably about 0.5 to 1.5 g / cnP, and especially about 0.75 to 1 g / cnP,

- mean diameter (derived from the cumulative overflow percentage) of about 0.4 to 1.8, preferably about 0.5 to 0.8 mm, with an additive logarithmic (log) standard deviation of 0.0 / 0, 5, preferably 0.05 to 0.3;

Weight ratio of residual accompanying water to 0: 0. If they are added to the silicate, expressed as dry matter, the v / v must be less than or equal to about 120: 100.

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The above-described process comprising a mixed granulation step, optionally a compacting step and a drying step makes it possible to obtain mixed granules based on alkali metal silicate hydrates and alkali metal carbonates which dissolve rapidly in water.

The dissolution rate of 90% and 95% of the mixed granulate according to the invention in water is less than 3 minutes, respectively. less than 5 minutes.

The dissolution rate of 90% and 95% of the mixed granulate in water is the time required to dissolve 90% or 95% of the product in water at 20 ° C to a concentration of 35 g / l ·

If the builder according to the invention has a defined structure (powder, mixed granulate and the like) then it is used in dishwasher detergent compositions in an amount of 3 to 90% by weight, preferably 3 to 70% by weight, based on the weight of said composition; the amount used in the compositions for washing machines is about 3 to 60%, preferably about 3 to 40, based on the weight of said composition (said amounts are expressed as silicate dry weight based on the weight of the composition).

In addition to the builder of the invention, at least one surfactant is present in the laundry composition in an amount of 8 to 20%, preferably about 10 to 15%, based on the weight of said composition.

The following surfactants may be mentioned:

anionic surfactants, such as alkali metal soaps (C 8 -C 24 fatty acid alkali metal salts), alkali metal sulphonates (C 8 -C 13 alkylbenzene sulphonates, C 12 -C 16 alkylsulphonates), oxyethylenated and sulphated fatty acids alcohols having 6 to 16 carbon atoms, oxyethylenated or sulfated alkyl phenols having 8 to 13 carbon atoms, sulfosuction16

alkali metal atoms /, etc., / alkylsulfosuccinates with carbon monoxide

- non-ionic surfactants such as polyoxyethylenated (C 6 -C 12) alkylphenols, oxyethylenated aliphatic alcohols (C 8 -C 22), ethylene oxide-propylene oxide block copolymers, and optionally polyoxyethylenated carboxylic acid amides,

- amphoteric surfactants such as alkyldimethyl betaines,

cationic surfactants such as alkyltrimethylammonium- or alkyldimethylethylammonium chlorides or bromides.

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In addition, various ingredients may be present in the laundry composition, including in particular:

- builders such as:

- phosphates in an amount of less than 25% of the total weight of the formulation,

- zeolites in an amount of 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 in an amount of up to about 10% of the total weight of the formulation,

- citric acid or tartaric acid in an amount of up to about 50% of the total weight of the formulation, the total amount of builder corresponding to about 0.2 to%, preferably 20 to 45, of the total weight of said detergent composition,

- Bleaching Agents * as perborate, percarbonate, chloroisocyanurates and Ν, Ν, Ν ', N' - tetraacetyl / TAED /, in an amount up to about JO% of the total weight of said detergent composition, »ϊ ^'f t s> -« ί . - «/ Λ? Ϊ * Γ.τν * ';

i. '; «.

- redeposition agents, such as carboxymethylcellulose olc:> methylcellulose, in an amount of up to about 5% of the total wt per night of said detergent composition,

anti-incrusting agents, such as lyic acid copolymer and maleic anhydride, in an amount in:. about% of the total weight of said detergent;

fillers, such as sodium sulfate for detergent powders, in an amount of up to about 50% of the total weight of the detergent composition.

In the following, the invention will be further elucidated by way of examples of specific 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

Example 1

Builder synthesis

Products used for this synthesis:

- sodium silicate: solution with molar ratio SiO2 / Na2O = 2.8, dry matter: 45% by weight, relative density: 15% distribution of polyanionic species (in molar percentages based on the total amount of silicon): Qq = 0 , 8%, Q _T = 6.2%, Q ₂ and Q ₃ Q ₄ = 83 = 10%.

- sodium carbonate: anhydrous powder, unsprayed bulk density: 1.1 g / cnP, particle size: d ^ _Q = 0.5 µm.

Custom synthesis:

To the sodium silicate solution heated to 80 ° C, pre-dissolved sodium carbonate was added with stirring. In this case, the addition of water to the sodium carbonate allows the washing; The mixture is treated with a mixed solution, the dry matter of which is identical to that of the starting silicate solution. The two components are mixed in such a proportion that the sodium carbonate content clarifies 30 l of the total silicate and carbonate solids.

The mixed solution is then dried in an oven for 20 hours at 20 ° C. The resulting solid is ground in a Forplex mill. The final stage of the synthesis consists of drying in a fluidized bed (fluidized bed) at a temperature of 30 to 40 ° C, which is carried out so as to obtain a solid product of the following composition:

- the proportion of sodium carbonate is 30% of the total dry matter of silicate and carbonate,

- the ratio by weight of residual accompanying water of silicate to silicate, expressed as dry matter, is 49,7: 100.

The product had the following properties: untamped packing density 0.8 g / cm @ \ particle size: 0.5 mm, d = 0.1 mm _Q1, d _9Q 1 mm, dissolution: less than 4 minutes for 99% dissolved product (conductometric measurement of an aqueous solution containing 3 g / l product at 20 ° C), calcium sequestering capacity: 197 mg CaCO 2 per gram of anhydrous product. This sequestering capacity is determined by measuring the residual calcium concentration at t = 15 minutes, wherein the product to be tested is introduced at t = 0 into a solution with a known calcium concentration (the solution is controlled to pH 10).

Example 2

Preparation of mixed granulate

Products used:

- sodium silicate solution: SiCl2 / Na2O = 2.0 molar ratio, dry matter: 45.5% by weight, density - 1.54 g / crP,

- sprayed silicate: the molar ratio of Si0 ₂ / FIA ₇ 0 - 2.05, dry basis - 20%, density - 0.55 g / ^cm-1 particle size; = 0, 2 mih,

- sodium carbonate: light soda, density = 0.6 g / cnP, particle size: d ^ Q = 0.12 mm.

A solution containing 38% by weight of carbonate (based on the total dry matter of silicate and carbonate) is prepared at 80 ° C by mixing the carbonate solution into a silicate solution with the stated molar ratio of 2. The dry weight of the thus prepared mixed solution is 37.7% *

Granulation of this solution is carried out in a drum having a length of 1300 mm and a diameter of 500 mm and rotating at a speed of 20 rpm. Granulation is initiated through a stock bed consisting of a ground mixture of light carbonate and sprayed silicate with a molar ratio of 2. The composition of the carbonate and silicate in this mixture is identical to that of the mixed solution. The actual granulation is carried out in the first part of the drum in which the solution is sprayed onto the powder bed by means of a pipe sprayer. Drying is carried out in the second part of the drum, which is equipped with a hoist and through which hot air is guided in countercurrent.

Granulation, compaction and drying are thus carried out in one and the same plant. The product leaving the drum is partially recycled after grinding and screening on a 0.2 to 1.25 mm sieve to enter the drum. In this way, when the steady state is reached, the initial storage bed is completely replaced by the newly manufactured product and the granulation process then has the following parameters:

- feed solution: 6 to 8 l / h,

- powder supply (recycling): 50 kg / h,

- wetting ratio: 0,12 to 0,16 l / kg,

- amount of drying air supplied: 110 to 120 m ^ / h,

- drying air temperature: 105 to 110 ° C,

- residence time in the drum: 30 to 40 minutes.

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The mixed granulate thus obtained has the following pile ¹ nose ti:

- the carbonate / silicate ratio, expressed in dry matter, . both components: 39:62,

- ratio of silicate water to silicate, expressed as dry matter: 51: 100,

- unshaked bulk density: 0,89 g / cnP,

- particle size: = 0.45 µm, dg ^ = 0.8 mm with a decimal standard deviation of 0.37 ·

The granulate obtained has the following dissolution times:

- 90% by weight of the product is dissolved in 50 seconds (aqueous solution at 35 g / l at 20 ° C),

- 95% by weight of the product is dissolved in 67 seconds (aqueous solution at 35 g / l at 20 ° 0),

- 99% by weight of the product is dissolved in 154 seconds (35 g / l aqueous solution at 20 ° C).

By way of comparison, the following dissolution times were determined for a simple dry starting mixture of carbonate and sprayed silicate forming initially said storage bed, which do not fall within the scope of the invention:

- 90% by weight of the product is dissolved in 55 seconds (aqueous solution at 35 g / l at 20 ° C),

- 95% by weight of the product is dissolved in 108 seconds (aqueous solution at 35 g / l at 20 ° C),

- 99% by weight of the product is dissolved in 266 seconds (35 g / l aqueous solution at 20 ° C).

The calcium sequestering capacity of the obtained mixed granulate is 243-249 mg of C'aCO ^ per gram of anhydrous product. This sequestering capacity is determined as in Example 1.

Example 3

Preparation of mixed granulate

A granulation process analogous to that of Example 2 is used, except that:. The process is carried out in an open loop, which means that a dry mixture of carbonate and sprayed silicate and said mixed solution and the product obtained are not recycled to the granulating apparatus. Likewise, drying is carried out analogously.

The following granulation process parameters are used:

- mixed solution feed: 6 to 8 l / h,

- powder supply: 30 kg / h,

- wetting ratio: 0,2 to 0,27 l / kg,

- amount of drying air supplied: 110 to 120 m ^ / h,

- drying air temperature: 105 to 110 ° C,

- residence time in the drum: 30 to 40 minutes.

The mixture granulate thus obtained has the following properties:

- carbonate / silicate ratio, expressed in dry matter of both components: 37:63,

the ratio of silicate to silicate accompanying water, expressed as dry matter; 42: 100,

- unsharried bulk density: 0,54 g / cm · ^,

particle size: = 0.57 mm, d ^ = 0.78 mm, with a standard logarithmic standard deviation of 0.12.

The granulate obtained has the following dissolution times:

- 90% by weight of the product is dissolved in 55 seconds (aqueous solution at 35 g / l at 20 ° C),

- 95% by weight of the product is dissolved in 122 seconds (35 g / l aqueous solution at 20 ° C),

- 99% by weight of the product is dissolved in 300 seconds (35 g / l at 20 ° 0).

The calcium sequestering capacity of the obtained mixed granulate is 245 mg CaCO 2 per gram of anhydrous product. This sequestering capacity was determined as in Example 1.

These blended granules are dry blended with the other ingredients in amounts such that the following laundry detergent composition is obtained:

Detergent composition

Component ____ Contents / parts by weight /

The granulate obtained

Sokalan (ΣΡ5 / BASF copolymer /

Thixolex 25 (amorphous aluminosilicate from Rhone-Poulenc)

Sodium sulphate

TAED

LAB / 80%

Synperonic A3

Synperonic A9

Esperase / Enzyme Novo /

Tiimopal DMSX

Tinopal SOP / C.iba-Gei Brightener

carboxymethylcellulose

0.3

0.2

0.2

2.5

A test to determine the effectiveness of the detergent composition in soil removal is performed in a Wascator FOM 71 r using the following test conditions;

- cycle used: 60 ° C,

- total cycle time: 70 minutes; without prewash

- number of cycles: 3 per wash,

- water hardness: 32 French degrees of hardness,

- washing machine: 3,5 kg white cotton rags, cl

- test fabrics: two series of the following 3 fabrics are introduced into the washing machine, which are squeezed with the following cotton rags: raw cotton: test fabric

Krefeld 10 C

IEC 106

EMPA 101 polyester / raw cotton test fabric

Krefeld 20 C

EMPA 104 protein spots blood / EMPA 111 / cocoa / EMPA 112 / blend / EMPA 116 / oxidizable spots Tea / Krefeld 10 G / unbleached cotton / EMPA 222 / wine / EMPA 114 /.

- detergent dosing:

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

Method of measuring washing of dirt and stains

Determination of the percentage of impurity removal is made by photometric measurements (measurement of the amount of light reflected off the fabric). The Datacalor Elrepho 2000 is used for these measurements.

The percentage removal of dirt is expressed by the following formula:

C - B

Dirt removal /% / = -----------— x 100,

A - B where:

A means the reflectance of the control white sample,

B · means reflectance of the dirty sample,

C means the reflectance of the dirty sample after washing.

The reflectance values are determined using a blue trichromatic component without optical brighteners.

.Number of measurements per sample ··· number of samples per wash number of washes

4.

2

3, which means 4 x 2 x 3 = measurements for each type of dirt, for each product and for each concentration tested.

A test for evaluating the anti-encrusting properties of the laundry composition is performed in a Schultess Super 6 De Luxe r drum washer using the following test conditions:

- cycle used: 60 ° C,

- total cycle time: 65 minutes? without prewash

- number of cycles; 25 cumulative washes,

- water hardness: 21,2 French hardness grade,

test fabric used: control strip exactly conforming to the specifications for

NFT standard 73 * 600

- washing machine load: 3 kg 100% cotton looped / terry / bath towels,

- detergent dosage: 5 g / l *

Test strips that have been subjected to 25 washes dry. they are then weighed and calcined at a temperature of 900 ° C to determine the percentage weight of ash relative to the initial weight of the test strip. The results of the individual tests are shown in Table I below.

Comparative Example 4

Preparation of mixed granulate

The granulation system consists of a drum analogous to that described in Example 2 and rotating at a rpm. Adjust the bar at the drum outlet so that:. that the residence time of the particle in the granulation drum is about 15 to 15. 20 minutes.

<> U - - * ·. C

- c? .IN. '' i · _t I

The powder is fed to the drum at a rate of 37 kg / h carbonates / powder having the same characteristics as the powders of Example 2. To this powder rolling in the drum at a rate of 18 l / hb is sprayed at 80 ° C silicates; which is identical to the solution of Example 2, using air of 80 ° C and using a double flat nozzle, located in the first third of the drum.

The mixed granulate leaving the drum has an ambient temperature and a density of 0.68 g / cm \. is 20 rpm.

The granulate so obtained is then dried in a fluidized bed at a temperature of about 65 ° C (the air temperature of the granulating air is 70 ° C) for 15 minutes.

The product thus dried has the following characteristics:

- carbonate / silicate ratio expressed in dry matter of both components: 66: 34j

- ratio of silicate water to silicate, expressed as dry matter: 61: 100,

calcium sequestration capacity: 285 mg CaCO-j per gram of anhydrous product; this sequestering capacity is determined as in Example 1.

The granulate obtained has an excellent storage behavior.

This blended granulate is then dry blended with the laxatives in amounts to provide a laundry detergent composition that is identical to the composition described in Example 4 (except blended granules).

Also, this laundry composition is subjected to tests to determine soil removal efficiency and anti-crust properties of the composition. The results obtained are also shown in Table I below.

Porovnáv.príklad 4 Example 3 ' .Incrustation 5 g / l 3.72 2.88 They work efficiency Crude cotton 5 g / 1 40 ° C 32.2 32.9 8 g / 140 ° C 47 41.9 5 g / 60 ° C ' 51.4 49  8 g / 60 ° C:  . 56.3 54.8 46.73 44.65 Polyester / raw cotton 5 g / 1 40 ° C 39.2 35.3 8 g / 140 ° C 56.1 50.1 : 5 g / 1 60 ° σ 56.8 55.7 8 g / 1 60 ° C 65.4 62.3 • 54.38 50.85 Protein spots 5 g / 1 40 ° C 38.8 34.8 ’’ 8 g / 1 40 ° σ 46.3 40.2 5 g / 1 60 ° C 50.6 51 ..... 8 g / 1 60 ° C 58.6 56.4 48.58 45.60 Oxidizable Stains 5g / l 40 ° C 42.1 42.1 6 g / 140 ° C 59.5. ...... 55 5 g / 1 60 ° σ 75.7 72.8 8 g / 1 60 ° C 83.8 62 ¹ ...... ........... 73 69.93 .... 'Overall efficiency 55.67 5,2.76

Claims (19)

1. Builče rYpre ^_ detergent composition, characterized en characterized in that it comprises an aqueous solution of alkali metal silicate with a molar ratio Si0 ₂ / M ₂ 0 of about 1.6 to 4 and of an inorganic product that is inert towards the said silicate and is miscible with said silicate solution, wherein the product represents 5 to less than 55 of the total dry weight and the ratio of residual silicate accompanying water to silicate dry weight is greater than or equal to 33: 100, preferably 36: 100, wherein M is an alkali metal. Builder according to claim 1, characterized in that the inorganic product is sodium carbonate, sodium sulfate, sodium borate, sodium perborate, sodium metasilicate, phosphate or polyphosphate such as sodium orthophosphate and sodium tripolyphosphate, which products are present individually or in a mixture. Builder according to claim 1 or 2, characterized in that the inorganic product represents 20 to 40% of the total dry weight. Builder according to one of the preceding claims, characterized in that the aqueous alkali metal silicate solution has a silicate dry matter content of about 10 to 60%, preferably about 35 to 50%. Builder according to any one of the preceding claims, characterized in that the weight ratio of residual silicate accompanying water to silicate dry matter is less than or equal to 120: 100. 6. Builder according to any one of the previous i.ch Ni-b t.kov, characterized in that the molar ratio of SiO ₂ / M ₂ O is equal to the silicate of 1.8 to 3.5, wherein wl is an alkali metal 7 »Mixed granulate of alkali metal silicate hydrates and alkali metal carbonates, characterized in that it can be obtained by a process comprising: and / spraying an aqueous solution consisting of a mixture of an aqueous solution of alkali metal silicate having a SiO ₂ í ₂ O molar ratio of about 1.6 to 4, preferably about 1.8 to 3.5, and an alkali metal carbonate, said carbonate being 5 to less than 55 % of the total weight of dry matter, on a rolling bed of particles identical in composition to the spray mixture and passing through a rotary granulation device, the speed of the particles, the thickness of the rolling bed and the quantity of spray solution to be selected such that and / or optionally drying said blended granules obtained in step a /, wherein said steps are carried out such that the weight ratio of silicate to water of silicate is greater than or equal to 33: 100, preferably 36: 100, and M represents an alkali metal. Mixed granulate according to claim 7, characterized in that the alkali metal silicate and alkali metal carbonate are sodium or potassium silicate and carbonate, preferably sodium silicate and carbonate. Mixed granulate according to claim 7 or 8, characterized in that between the stages a / and b) the mixed granulate obtained in step a / is subjected to a compacting treatment. Mixed granulate according to one of the preceding claims 7 to 9, characterized in that the silicate solution has a silicate dry matter content of about 10 to 60%, preferably about. 39 to 50%. 11. The mixed granulate according to any one of the preceding claims. 7. The process of claim 7, wherein step (a) is carried out at a temperature of about 20 to 95 ° C. Mixed granulate according to one of the preceding claims 7 to 11, characterized in that the particles having a composition identical to that of the spray mixture are obtained by drying a solution identical to said aqueous solution consisting of an alkali metal silicate and carbonate. Mixed granulate according to one of the preceding claims 7 to 12, characterized in that the granulating device is a rotary granulator enabling the particles to pass in a thin layer. Mixed granulate according to claim 13, characterized in that the rotary granulator is a pelletizer. I Mixed granulate according to one of the preceding claims 7 to 12, characterized in that the granulation device is a drum granulation device. Mixed granulate according to one of the preceding claims 7 to 15, characterized in that the particles having a composition identical to that of the spray mixture are passed through a granulating device at a temperature of about 15 to 200 ° C. Mixed granulate according to any one of the preceding claims 7 to 16, characterized in that the amount of the silicate / carbonate solution to be sprayed and the silicate / carbonate mixture to be used corresponds to the ratio of liquid to feed rate. -. a particle size in the range of from 0.05 to 0.8 l / kg, preferably from 0.1 to 0.8 l / kg 0.5 l / kg, these values refer to sodium salts. 18. The mixed granulate according to any of the preceding claims - 30 years 7 to 17, characterized in that the compaction treatment is carried out at ambient temperature by the rolling movement of the axial granulate obtained in step a /, in the rotary heat pump, f. 19 · Spherical mixed granulate 11a hydrate-based base ···, k: alkali metal mercurates and alkali metal carbonate, characterized in that it has: an alkali metal silicate, in particular potassium or potassium, adsorbed and / or absorbed 11a alkali metal carbonate, said carbonate representing 5 to less than 55% of the weight of adsorbed and / or absorbed silicate and the weight ratio of residual accompanying water the silicate to the silicate dry matter is greater than or equal to 33: 100, preferably 36: 100, - nestrašenú bulk density of 0.4 to 1.5 g / cm \ ^Q, preferably about 0.5, from 1.5 g / cm ^, and especially about 0.75 to 1 g / CNP, and a mean particle diameter of about 0.4 to 1.8 mm, preferably about 0.5 to 0.8 mm, with a decimal logarithmic standard deviation of 0.02 to 0.5, preferably 0.05 to 0.3,