CA2056674C - Alkaline metal silicate based builder for detergent compositions - Google Patents

Abstract

Builder agent for powdered detergent composition, consisting of an alkali metal silicate rich in silicon atoms in the Q2 and Q3 form. A solution of alkali metal silicate with an SiO2/M2O ratio of 1.6 to 3.5 which, as such, has a solids content of 10 - 60 % or which is in supported form, especially in the form of cogranulates, the weight ratio of silicate expressed on dry basis/water associated with the silicate ranging from 100/120 to 100/40, is an example of a silicate rich in silicon atoms in the Q2 and Q3 form. Use in powdered detergent compositions, especially for a washing machine and for a dishwasher.

Description

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BUILDER AGENT BASED ON ALKALINE METAL SILICATES
FOR DETERGENT COMPOSITIONS
The subject of the present invention is a builder agent consisting of alkali metal silicates rich in species in which the silicon atoms are in Q2 and Q3 form, intended for compositions Detergent; .particularly to powdered detergents especially for washing machine or dishwasher.
"Builder" means any active adjuvant which improves the performance of surfactants of a detergent composition.
The builder must have a so-called "softening" effect on the water used for washing. He must therefore eliminate the calcium and magnesium which are present in water as soluble salts, and in soiled linen in more or less complex forms 1.5 soluble. The elimination of calcium and magnesium can be done either by complexation, in the form of soluble species, or by exchange of ions, either by precipitation. If it is precipitation, it must be checked to avoid encrustation on linen or parts of washing machines.
~ 0 This control of precipitation is obtained in particular by water-soluble polymers with an affinity for calcium and magnesium.
It is also necessary that the builder adds to the emulsifying effect of surfactants vis-à-vis fatty stains, a dispersing effect ? 5 vis-à-vis "pigmentary" stains such as metal oxides, clays, silica; various dusts, humus, limestone, soot and the like.
. This dispersing effect is generally obtained thanks to the presence of polyanions, bringing a high density of negative charges to the 30 interfaces.
It is also necessary that the builder brings an ionic force favorable to the functioning of surfactants, in particular by increasing the micelle size.
It must also provide OH- ions, for the 35 saponification of fats and again, for increased loads negative surface of textile surfaces and stains particulate. ' Y
mea Silicates have long been considered good detergency builders, but are currently less used in phosphate-free compositions for washing machines.
The most used silicates in this application are those having a SiO2 / Na20 molar ratio of between 1.6 and 2.4.
They are marketed either as concentrated solutions at 35 -45% by weight of dry extract, or in the form of silicate in atomized powder and possibly compacted.
Concentrated commercial solutions are most often prepared from completely amorphous "glassy" silicate, also called "water glass".
These soluble glasses are water-solubilized in an autoclave under pressure at 140 ° C. Commercial solutions are thus obtained with . a dry extract of 45% by weight approximately for a silicate of ratio 2 and l: 5 approximately 35% for a silicate of ratio 3.5.
The concentrated silicate solutions are introduced by the detergent formulator in the aqueous suspension (slurry) containing The other components from 1 to 1 essi ve. The sl urry is then dried by atomization. Silicate, coatomised and co-dried with others constituents, contains only 20% of associated water compared to at its dry weight, or even less.
As for the commercial silicate powder, it is obtained by drying by atomization of concentrated solutions of glassy silicate; he is necessary to conserve 20 to 22% by weight of water relative to the product finished to ensure good solubility of said product.
It has been found that when dissolved in a washing in the proportion of 1 to 3 g / liter, this powdered silicate which does not contains only 20 to 22% by weight of associated water (relative to the product finished), has only weak builder properties.
Indeed, this powdered silicate in solution generates essentially monomeric silicic species of formula Si (OX) 4 where X
represents H or Na, having no builder effect. Such species monomers cannot reassociate with each other to form polyanions only if the silicate concentration is at least 50 to 500 g / liter and this slowly.
Such silicate concentrations as well as the slow kinetics of polymerization of the monomeric species are not compatible with conditions and times of washing in a washing machine.

What has been found for a powder containing 20 22 ~ chemically associated water (compared to the finished product) is of course valid for formulations containing a silicate with 20% associated water (compared to dry silicate) prepared by introducing a concentrated solution of silicate in a slurry, then drying.
The Applicant has found that when a silicate of alkali metal is rich in species in which atoms of silicon are in the form QZ and Q3, the polyanionic species formed by dilution up to 1 to 3 g / 1 in a washing medium have a sufficient lifespan to allow them to play a role of "builder" in deterrence.
The expression "silicon atoms in Q2 and Q3 form"
is a representation of the degree of association of the atoms of silicon between them; "Q2" means that each silicon atom participates in two links -Si-O-Si-, the two links remaining being a termination -Si-0-X where X is a metal alkaline or H; "Q3" _ means that each silicon atom participates in three -Si-O-Si- bonds, the remaining bond being a termination -Si-OX.
The builder agent for detergent composition, subject of the invention is characterized in that it is consisting of an alkali metal silicate, especially sodium or potassium, containing at least 30â, preferably at least 506 of silicon atoms in Q2 and Q3 form.
Said silicate may have a molar ratio Si02 / M20 of the order of 1.6 to 3.5, preferably of the order of 1.8 to 2.6 where M is an alkali metal.
Said builder agent can appear under a any form, structured (powder, granules ...) or not.
A first embodiment of the invention is a builder agent consisting of approximately an aqueous solution 10-60ô, preferably about 35-50ô by weight of dry extract of an alkali metal silicate, in particular of sodium or of potassium, Si02 / M20 molar ratio of the order of 1.6 to 3.5, preferably in the range of 1.8 to 2.6.

2056ô ~ '4 The concentrated solution of alkali metal silicate used as builder agent is preferably obtained by water-solubilization of "soluble glasses" in an autoclave under pressure at 140 ° C, then possible dilution it can also be defeated by other known means, such as attack direct sand with caustic soda in solution concentrated.
NMR analysis shows that:
~ 45 ° solution of dry silicate extract l0 glassy molar ratio Si02 / Na20 = 2 contains 346 species Q3, 51% of Q2 species, 12% of Ql species and 3% of Qp species.
~ a solution of 35 ~ dry extract of ratio 3.5 contains 46 ~ Q3 species, 27 ~ Q2 species, 16 ~ Q species, ~, 9 ~ Q1 species and 2 ~ Qp species.
Said builder solution can be used in post addition by spraying on the washing powder of "bottom of tower "in the case of an installation by atomization or on the mixture of the components of the washing formula in the case dry mixing, within the limit of adsorption capacity 20 powders. The powder mixture obtained can be spaded moderately if necessary, so that the weight ratio dry silicate / remaining water associated with silicate is included between 100/120 and 100/40, preferably between 100/90 and 100/50.
The amount of silicate solution that can be used in use is such that the dry silicate / powder weight ratio detergent is between 1/100 and 30/100, preferably in the range of 10/100 to 20/100.
Another non-limiting mode of realization of the invention consists of an aqueous solution at approximately l0-60 ~, 30 preferably about 35-50 ~ by weight of dry extract of a alkali metal silicate, in particular sodium or potassium, of Sio2 / M20 molar ratio of the order of 1.6 to 3.5, of preferably of the order of 1.8 to 2.6 where M is an alkali metal, adsorbed and / or absorbed on an inert particulate support with respect to silicate, the silicate weight ratio expressed in dry / remaining water associated with silicate ranging from 100/120 to NOT

4a 100/40, preferably ranging from 100/90 to 100/50.
"Inert" means chemically inert.
The term water "associated" with silicate means water from the supported solution which is not combined with mineral support, especially in the form of crystallized hydrate.
Among the inorganic supports of the solution of silicate, there may be mentioned compounds preferably hydro-soluble such as: sodium carbonate, sulphate sodium, sodium borate, sodium perborate, sodium metasilicate, phosphates or polyphosphates such than trisodium phosphate, with the exception of tripolyphosphate sodium, these supports being present alone or as a mixture between them.
at.

The support generally represents around 55 to ~ 95%; of preferably around 65 to 85% of the weight of the supported solution expressed in dry (i.e. weight of solution expressed in dry + weight of support).
5 Said supported solution can be prepared by adsorption and / or absorption by contacting a concentrated aqueous solution of a alkali metal silicate - Si02 / M20 molar ratio of the order of 1.6 to 3.5, preferably of the order of 1.8 to 2.6, and having an extract dry of the order of 10 to 60 ~%, preferably of the order of 35 to 50%, with an inert inorganic support with respect to silicate, said support being present in quantity such as the quantity of water remaining associated with said silicate after adsorption and / or absorption corresponds to a ratio weight silicate expressed in.sec / water associated with silicate of the order of 100/120 to 100/40, preferably of the order of 100/90 to 100/50.
: 15 The contacting operation can be carried out by addition, in particular by spraying, said concentrated silicate solution on the support in particulate form, in any known mixer shear, in particular of the LODIGE ~ type, or in the granulation (drum, plate ...) ..., at a temperature of the order of 20 to 95 ° C, preferably of the order of 70 to 95 ° C.
The supports that can be used are those already mentioned in the list above.
The quantity and concentration of the silicate solution to be used used are a function of the absorbent and / or adsorbent capacity of the support, taking into account a possible possibility for said support especially form crystallizable hydrates; the water rate not associated with silicate which may be in the form of a hydrate in the support can be determined in a known manner by thermal analysis differential or by quantitative X-ray diffraction. Water eventually combined with support in forms other than defined hydrates can be determined by appropriate physico-chemical methods (thermoporosimetry, thermogravimetry, proton NMR, IR).
The limit of absorbent and / or adsorbent capacity of said support can be determined according to known methods, for example by measuring the evolution of the angle at the base of the landslide as a function of the rate of addition of the silicate solution.

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If necessary, the mixture consisting of the support and the solution of silicate can itself be dried, but moderately so as to obtain the desired proportions of water associated with the silicate.
The particles of supported silicate solution obtained can be ground, if desired, so as to obtain an average diameter of in the range of 200 to 800 micrometers.
Alkali metal silicate solutions in adsorbed form and / or absorbed on an alkali metal carbonate and occurring under form of spherical cogranules of hydrated alkali metal silicate and of alkali metal carbonate are builder agents of the invention particularly efficient.
Said spherical cogranules of hydrated metal silicates alkali and alkali metal carbonates, can be prepared according to a process characterized in that - an aqueous solution is sprayed based on si 1 i cates of metals alkaline or based on a mixture of silicates and metal carbonates alkaline ~ on a moving bed of particles based on metal carbonates alkaline scrolling in a rotary granulating device, the speed movement of the particles, the thickness of the moving bed and the flow of the sprayed solution being such that each particle is transformed into a plastic co-granule by coming into contact with other particles, - the cogranules obtained are subjected to a densification operation, - said densified cogranules are dried, until a content is obtained in water associated with silicate corresponding to a silicate weight ratio expressed in dry / water associated with the silicate of the order of 100/120 to 100/40.
Among the alkali metal silicates and carbonates, preferably quote those of sodium and potassium, and all especially those of sodium.
Aqueous solution based on silicate or mixture sprayed silicate / carbonate may have a dry extract content of around 30 to 55% by weight, preferably 30 to 45% by weight said alkali metal silicate has a SiO2 / M20 molar ratio of in the range of 1.6 to 3.5, preferably in the range of 1, S to 2.6 and all particularly close to 2; said carbonate can optionally be present in proportions depending on the desired end product.
Spraying the silicate solution or mixture silicate / carbonate is produced at a temperature of the order of 20 to 95 ° C, preferably of the order of 70 to 95 ° C; this one maybe favored by joint introduction (for example using of a two-fluid nozzle) of pressurized air at a temperature of same order.
The particles used to prepare the co-granulates are mainly composed of carbonate alkali metal having:
~ an average diameter of the order of 10 to 150 microns, preferably in the range of 20 to 100 microns and all particularly close to 30 to 80 microns, ~ a non-packed filling density (non bulk density) of the order of 0.4 to i, lg / cm3, preferably around 0.6 to 1.1 g / cm3, ~ a water content of the order of 0.05 to 0.4%, preferably of the order of 0.1 to 0.3% by weight, ~ a rate of insoluble matter of the order of 5 at 100 mg / kg, generally in the range of 10 to 60 mg / kg.
Common milled or unground carbonate qualities can be implemented.
Next to these carbonate particles can be present small amounts (less than 10% of the weight of cogranulates ~) from to. minus a particulate detergent additive other nature, such as anti-depositing polymers (carboxymethyl - cellulose ...), enzymes ... commonly used in the detergency field, presenting a diameter and density close to those of the particles of carbonate.
The device used to carry out the operation spray co-granulation can be any device rotary type of rotating plate, bezel, drum rotary, mixer-granulator, rotary granulator ...
A first preferential mode of realization of these co-granulated consists in using a rotary granulator allowing the particles to travel in a thin layer. The beziers with an inclined axis of rotation relative to horizontal at an angle greater than 20 °, preferably w not 7a greater than 40 °, are particularly well suited; their geometry can be very diverse: frusto-conical, flat, in staircase, a combination of these three forms ...
A second preferred embodiment of these co-granulated consists in using a rotary drum, the angle of which inclination is at least 3 3 and preferably at least 5 ~.
The carbonate-based particles pass at a temperature _ "
'8 -, around 15 to 200 ° C, preferably around 15 to 120 ° C and all particularly of the order of 15 to 30 ° C.
Amounts of silicate solution or mixture silicate / carbonate to be sprayed and particles based on carbonate to be sprayed implement correspond to a liquid flow / flow rate of particles ranging from 0.2 to 0.8 1 / kg; preferably 0.4 to 0.7 1 / kg and especially from 0.62 to 0.7 1 / kg, these values being expressed as sodium salts.
The flow rate of the sprayed solution, the running speed of particles as well as the thickness of the particle layer in scrolling are such that each particle absorbs liquid and agglomerates with the other particles with which it comes into contact in order to obtain plastic granules and not a paste.
The speed of the particles and the thickness of the layer are regulated by the rate of introduction of the particles into the granulation device and the characteristics of the latter.
The residence time of the particles in a device of the type plate or drum is generally around 15 to 40 minutes.
It is within the reach of the skilled person, depending on a material first data, to adapt the characteristics of the device used 9 namely for a bezel . its geometry (truncated, flat, stepped, or combination of three forms), . its dimensions (depth, diameter), . its angle of inclination, . its speed of rotation, . the relative positions of the solid and liquid.
For a drum . its geometry (tube diameter) . its angle of inclination . its rotation speed . tube load . the relative positions of the solid and liquid.
The non-densified and undried cogranules obtained have characteristics depending on the conditions used to achieve g granulation. They usually present a silicate content of the order of 7 to 30% by weight, preferably of the order of 11 to 23% by weight, and very particularly of around 21 to 23% by weight, . a carbonate content of the order of 4% to 75% by weight, preferably of the order of 48 to 64% by weight and very particularly of around 48 to 51% ~ by weight, a water content of the order of 18 to 29%, preferably of on the order of 25 to 29% by weight, and very particularly on the order of 27 to 29% by weight.
The densification operation can be carried out at temperature ambient for rolling of the cogranules obtained at the granulation stage in a rotating device.
This device is preferably independent of that of a5 granulation.
This densification step can advantageously be carried out by introduction and stay of the cogranules in a rotary drum. The angle inclination of the latter is at least 3%, preferably at least 5%. The dimensions of this drum, its speed of rotation and the time of stay of the cogranules are a function of the desired density; time of stay is generally of the order of 20 minutes to 3 hours, from preferably around 20 to 90 minutes.
Mixer-granulators are also well suited for this densification operation.
Co-granulation and densification operations can be done also be performed in the same device, for example in a staircase bezel, the densification of the cogranules being obtained by rolling of said cogranules on the last steps of the apparatus;
similarly these two operations can be carried out in a drum : 30 two sections.
The densified cogranules are then dried by any known means.
A particularly effective method is drying in a fluidized bed using an air stream at a temperature of the order of 40 to 90 ° C, preferably from 60 to 80 ° C. This operation is carried out during a : 35 duration depending on air temperature, water content of co-granulated at the outlet of the granulation device and that desired dried cogranules, as well as fluidization conditions;

r '~, o r i0 2056674 the skilled person knows how to adapt these different conditions to product sought.
Dried dense cogranules generally have:
- a silicate content of Sio2 / M2o ratio where M is an alkali metal of 1.6 to 3.5, of the order of 8 to 38 ~ by weight, preferably of the order of 14 to 31 ~ by weight, and any particu in the order of 24 to 31 ~ by weight, - a carbonate content of the order of 47 to 87 ~ in weight, preferably in the range of 59 to 81 ~ by weight, all particularly of the order of 64 to 69 ~ by weight, - a water content of the order of 5 to 25 ~ by weight, preferably of the order of 7 to 20 ~ by weight, and any particular from 12 to 20% by weight, - an uncompressed filling density of the order of 0.7 to 1.5 g / cm3 preferably of the order of 0.75 to 1.5 g / cm3 and especially around 0.8 to lg / cm3, - a median diameter (in the sense of the percentages cumulative passers) of the order of 0.4 to 1.8 mm, preferably of the order of 0.6 to 0.8 mm, with a standard deviation log10 of 0.02 to 0.3, preferably from 0.05 to 0.1.
These cogranulation / densification / drying stages make it possible to obtain cogranules based on silicates hydrates of alkali metals and alkali metal carbonates perfectly spherical, dense and dissolving quickly in water.
These cogranules obtained after drying can be added, by spraying, small amounts of liquid compounds commonly used in the field of detergency.
Spherical cogranules based on silicates hydrates of sodium and sodium carbonate particularly suitable for the preparation of detergent compositions for dishwasher and washing machine are the ones with the following features:

- loa - 2056674 - uneteneurensi 1 icate of molar ratio Si02 / Na2U of 1.8 to 2.6 and in the range of $ 24 to $ 31 by weight, - a carbonate content of the order of 64 to 69 in weight, - a water content of 12 to 20% by weight, - an unfilled filling density of the order from 0.7 to 1.5 g / cm3, preferably of the order of 0.8 to 1, - a median diameter of the order of 0.4 to 0.8 mm, with standard deviation 1og10 from 0.05 to 0.1, - a dissolution rate of 90% in water less than 2 minutes and 95% less than 4 minutes.
By dissolution rate is understood to be 90 ~ or 95 ~
in water, the time required to dissolve 90 ~ or 95 ~ of produced at a m 11 2 ~ 5667 ~
concentration of 35 g / 1 in water at 20 ° C.
- When it is structured (powder, co-granulated ...) the "builder" agent of the invention is used in detergent compositions for dishwasher at a rate of 3 to 90% by weight, preferably from 3 to 70 by weight of said compositions; the quantities used in compositions for washing machines are of the order of 3 to 60%, preferably of the order of 3 to 40% of the weight of said compositions (these quantities are expressed by weight of dry silicate relative to the weight of composition).
Next to the builder agent which is the subject of the invention is present in the detergent composition at least one surfactant in an amount which can range from 8 to 20%, preferably of the order of 10 to % of the weight of said composition.
Among these surfactants, mention may be made of 15 - anionic surfactants of the metal soap type alkaline (alkaline salts of Cg - C24 fatty acids), alkaline sulfonates (Cg - C13 alkylbenzene sulfonates, C12 - C16 alkylsulfonates) oxyethylenated and sulphated C6 - C16 fatty alcohols; Cg alkylphenols -C13 oxyethylenated and sulfated, alkali sulfosuccinates (alkyl-2p sulfosuccinates in C12 - C16) ~~~
- non-ionic surfactants of the C6 alkylphenol type - C12 polyoxyethylenated, aliphatic alcohols in Cg - C22 oxyethylenated, ethylene oxide block copolymers - oxide, propylene, amides optionally polyoxyethylenated carboxylic, - amphoteric surfactants of the alkylmethyl type betaine, : - cationic surfactants of the chlorides type or alkyltrimethylammonium bromides, alkyldimethylethylammonium bromides.
Various constituents may also be present in the composition detergent such as - "builders" of the type . less than 25% of the total weight of formulation, . zeolites up to around 40% of the total formulation weight, . sodium carbonate up to about 80% of the total weight of formulation, . nitriloacetic acid up to about 10% of the total weight of formulation, 2p5b674 . citric acid, tartaric acid up to about 20% by weight total formulation, the total amount of "builder"
corresponding to about 0.2 to 80%, preferably 20 to 45%
the total weight of said detergent composition, - bleaching agents such as perborates, percarbonates, chloroisocyanurates, N, N, N ', N'-tetraacetylethylenediamine (TAED) up to approximately 30% of the total weight of said composition detergent, - anti-redeposition agents of the carboxymethylcellulose type, methylcellulose in amounts up to about 5% by weight total of said detergent composition, - anti-encrustation agents of the acid copolymer type acrylic and maleic anhydride in amounts up to 10 approximately of the total weight of said detergent composition, 1 ~; - loads of the sodium sulfate type for detergents powder in an amount up to 50% of the total weight of said detergent composition.
The following examples are given for information only and cannot be considered Range a limit of the domain and spirit of the invention.
EXAMPLES 1 to 5 "Builder" performances - a sodium silicate solution of molar ratio Si02 / Na20 = 2 to 45% ~ by weight of dry extract (example 2) - a sodium silicate solution of molar ratio Si02 / Na20 = 3.4 to 35% by weight of extract sec (example 4) are measured in a TERGOTOMETER (US Testing Company, Noboken, USA), in binary mixture with an anionic LABS surfactant (dodecyl benzene ALDRICH linear sodium sulfonate), reflectance measurements being carried out using a GARDNER reflectometer.
These performances are compared to those - LABS alone at 2 g / 1 (example 1) - an atomized silicate powder of ratio 2 containing 22 of water (i.e. 28.2% of water relative to dry silicate) (example 3) 'V ~, n' ~, - of an atomized silicate powder of ratio 3.4 containing 18.6 9 °
of water (i.e. 22.8 ~ ° of water relative to dry silicate) (example 5) implemented under the same conditions (4 g / 1).
The results of these measurements are shown in Table I
Measurement method Principle A simplified machine wash is simulated in a tergotometer, washing standard soiled tissue test tubes at 65 ° C, with a surfactant and the builder to test. Washing takes twenty minutes and measures the color of fabrics before and after washing. We make a "white", by washing the same type of test tubes with the surfactant alone, to evaluate the performance of the builder tested.
Operating mode The tergotometer is a device made up of 4 2 1 stainless steel pots on which pulsators are adapted which are set to 100 cycles per minute. The pots are placed in a water tank regulated at 65 ° C.
1) In each pot we put 11 hard tap water (34 ° TH French) When the water is at temperature, we introduce 5 x 10 X 12 cm white cotton 405 W style test tubes of the TEST FABRIC company.
- 5 test pieces of 10 X 12 cm of white polyester (PEC) of reference n ° 7435 of the company TEST FABRIC.

- 2 test tubes of 10 X 12 cm of soiled cotton EMPA (ink mixture china and olive oil) article 101 of the company GALLEN.
- 2 test tubes of 10 X 12 cm of cotton soiled red wine article 114 from the company GALLEN.
- 2 x 10 cm x 12 cm polyestercotton (PEC) soiled EMPA test tubes article 104 of the company GALLEN.

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2) The following 3 operations are carried out simultaneously . stopwatch start . start of agitation . addition of builder / surfactant mixture The builder is tested at 4 g / 1 (mass calculated as dry matter of product) and 2 g / l of LABS are added thereto. .

3) Rin ae When twenty minutes have passed, the washing water is discarded and the fabrics are rinsed with 3 X 11 of cold tap water.

4) Spinning and drying We wring out the test tubes and pre-dry them by spreading them out.
individually in absorbent paper. The fabrics are then passed twice in a freezer between two sheets of absorbent paper a temperature of around 110 ° C.

5) Color measurement The GARDNER device is calibrated by measuring zero on a plate our reserved for this purpose, then by reading values L, a, b on a standardized white plate of the same type as the black one.
L places the color in shades from white to black.
L = 100 corresponds to white test tube L = 0 corresponds to black test tube located the color in shades from green to red.
a> o: the color turns red.
a <o: the color turns to green b locates the color in shades from yellow to blue.
b> o: the color turns to yellow b <o: the color turns to blue go,,, 2 ~ 566 ~ 4 After calibration, the actual measurements are made. By pot on takes 2 test tubes from each tissue category, we make 5 measurements per test tube (i.e. one in the center and one at the four corners) in placing a heavy metal plate on the fabric, then averaging 5 arithmetic of the 10 determinations. We proceed in the same way with 1 unwashed fabrics.

6) Exploitation of results 10 DL and DE are calculated for each test and for each type of tissue.
DL = L after washing - L before washing Da = a before washing - a after washing Db = b after washing - b after washing 15 DE = DL2 + Da2 + Db2 '- Detergency We calculate 1 to average DL and DE for each product and each type of soiled fabric.
Then for each product, we calculate EMPA cotton det (ergonomics) = DE EMPA medium cotton Det (ergonomics) PEC EMPA = DE average PEC EMPA
Det (ergonomics) cotton YIN = DE medium cotton YIN
Cumulative det (ergence) = Sum of cotton detergents EMPA, PEC EMPA, cotton WINE
EXAMPLES 6 and 7 A LODIGE M5G ~ mixer (sold by LODIGE) is loaded 800 g anhydrous tripolyphosphate H2 ~ marketed by Rhône-Poulenc.
After closing and rotating the device at a speed of 400 rpm, 200 g of a solution of sodium silicate with Si02 / Na20 molar ratio = 2 to 45% extract dry.
This addition lasts 10 min; after an additional 10 minutes of mixing by rotation, the product is removed and left to stand for 2 h on a tray in the open air and at room temperature.

is The product features are as follows - TPP partially hydrated: 82% by weight - sodium silicate: 9% by weight - water associated with silicate. 9% by weight, i.e. I00% compared to silicate dry.
The amount of total water contained in the product by the measuring the weight loss of the latter by heating to 500 ° C; we IO also measures the amount of water bound in the form of hydrates by differential thermal analysis. The amount of associated water is calculated by difference between total water and bound water in the form hydrate.
- average diameter = 250 micrometers I5 The builder performance of this product is measured according to the method described above, however replacing the 2 PEC test pieces soiled EMPA article I04 by 2 WFK soiled cotton test tubes from the company KREFELD, with the same dimensions (example 6).
20 These performances are compared to those of a mixture of powders of TPP anhydrous H2 ~ and atomized silicate with Si02 / Na20 ratio = 2 to 22 of water, according to a TPP / dry silicate weight ratio of 800/90, and this in the same conditions (4 g / 1) (example 7).
The results of the measurements are shown in Table II.

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., ~, The granulation system consists of a flat plate of 800 mm diameter and 100 mm deep. During granulation, the rotation speed is around 35 rpm and the inclination of the axis of rotation relative to the horizontal is of the order of 55 °.
The plate to be granulated is fed continuously at a rate of 21.4 kg / h by a powder made up of fine particles of sodium carbonate, the main features are as follows - Title in alkalinity: 99.61 - water content (by weight) = 0.12% ~
unfilled filling density = 0.56g / cm3 - median diameter = 95 microns - insoluble rate = 58 mg / kg On this powder brought into rotation in the pellet plate is sprayed with air at 80 ° C a sodium silicate solution at a flow rate of 13.4 1 / h at a temperature of 80 ° C via a bi-fluid nozzle located at a distance of 20 cm from the bottom of the bezel. The active matter rate and the Si02 / Na20 molar ratio of the solution sprayed is 43% (by weight) and 2 respectively.
The average residence time of a particle in the plate is about 10 to 15 minutes. The temperature of the particles leaving the plate is the ambient temperature.
The pellets leaving the plate are introduced into a rotating tube with smooth walls of diameter 500 mm, length 1300mm and having a inclination on the order of 5%. The output diaphragm is adjusted by such that the average residence time of a particle is approximately 40 mins. The drum rotation speed (18 rpm) is chosen so to have a rolling bed of particles, which promotes densification of these.
The granules thus obtained are dried in a fluidized bed at a temperature of the order of 80 ° C. (temperature of the fluidizing air equal to 85 ° -90 ° C) for 10 to 15 minutes.
The product thus dried has the following characteristics - carbonate content (by weight) = 65 - silicate content (by weight) = 21% * 0.5 - water content (by weight) = 13.5 - filling density not packed = 0.90 g / cm3 -% by weight of refusal at 1 mm = 10.8 . ~~ ,,., - median diameter = 0.73 mm -% by weight from 0.2 mm = 6 - 90% (by weight) of the product dissolves in 50 s (aqueous solution to 35 g / 1 at 20 ° C), - 95 ~ ° (by weight) of the product dissolves in 65 s {solution: aqueous to 35 g / 1 at 20 ° C), - whiteness L = 96.3 - attrition resistance: 7%, The granules exhibit excellent storage behavior.
Measuring attrition resistance Material.
We use the flourometer, a standardized device used to qualify the hydraulic binders and described in the French standard P 15-443.
Procedure Sieve 50g of product between the 1200 and 180 micron sieve, using a ROTO-LAB ~ laboratory sieve shaker (marketed by PROLABO).
Recover the part between 180 and 1200 microns.
Weigh approximately exactly 25 g of the product to be tested; let M be the mass accurate.
Place them in the flourometer.
Weigh an empty Soxlhet ~ filter (marketed by PROLABO) and dry and place it at the top of the fluidization tube;
let M1 be its mass.
Fluidize for 5 min (dry air flow: 15 1 / min).
Recover the product flown in the filter as well as the fines possibly deposited on the vertical walls of the tube fluidization, using a swab of suitable diameter. Weigh ; is M2 the mass of these fines and the filter.
Sieve again on ROTO LA8 ~ the residue in the bottom of the tube fluidization and recover, for weighing, fines below 180 microns; let M3 be the mass of these fines.
Calculation. Expression of result The attrition rate is equal to the percentage of fines <180 microns formed during the fluidization time of the product.
Attrition ~ ° _ (M3 + M2-M1) X 100 M

~ M
'205Gb74 Example 9 The operations described in Example 1 are repeated, adding thereto the Only 5 following changes Granulation . pellet plate: rotation speed of 30 rpm, . powder feed: 22kg / h, . supply of silicate solution: 13 l / h.
10 Densification . drum rotation speed: .10 rpm, Fluid bed drying . temperature = 90 ° C, . duration: 20 min, 15 The dried product has the following characteristics - carbonate content (by weight) = 60.9%, - silicate content (by weight) = 22.9% t 0.5%, - water content (by weight) = 16.1 - unfilled filling density = 0.86 g / cm3 20 -% by weight of refusal at 1 mm = 2.6 - median diameter = 0.64 mm -% by weight going to 0.2 mm = 7.3 - 90% (by weight) of the product dissolves in 75 s (aqueous solution to 35 g / 1 at 20 ° C), - 95% (by weight) of the product dissolves in 102 s (aqueous solution at 35 g / 1 at ZO ° C), - whiteness L = 95.6 - attrition resistance: 9.2 The granules exhibit excellent storage behavior.
Example 10 The granulation system consists of a drum rotating at 40 rpm, with smooth walls, diameter 500 mm, length 1300 mm and with an inclination of around 7.5%. The output diaphragm is adjusted so that the average residence time of a particle or about 15 to 20 minutes.
The drum was invented continuously at a rate of 37 kg / h by a carbonate powder having the same characteristics as those of the powder of examples 1 and 2.

21 ' On this powder brought into rotation in the drum, is sprayed using air at 80 ° C via a bi-fluid jet nozzle dish located in the first third of the drum, a silicate solution (with an active ingredient content of 45.6% by weight and a ratio by weight Si02 / Na20 of 2) at 80 ° C with a flow rate of 18 l / h.
The cogranules at the outlet of the drum are at the temperature ambient and have a density of 0.68 g / cm3.
The cogranules are then densified batchwise for one hour in a smooth-walled rotary drum 500 mm in diameter, long 1300 mm and having an inclination of 5%.
The drum rotation speed is 20 rpm.
The granules thus obtained are dried in a fluidized bed at a temperature of the order of 65 ° C. (temperature of the fluidizing air equal to 70 ° C) for 15 min.
The dried product has the following characteristics - carbonate content (by weight) = 62%, - silicate content (by weight) = 20.5% 3 0.5%, - water content (by weight) = 17.6 - unfilled filling density = 0.820 -% by weight of refusal at 1 mm = 5%, - median diameter = 0.65 mm -% by weight going to 0.2 mm = 0.6 - 90% (by weight) of the product dissolves in 50 s (aqueous solution to g / 1 at 20 ° C), - 95% (by weight) of the product dissolves in 63 s (aqueous solution to 35 g / 1 at 20 ° C), The granules exhibit excellent storage behavior.
Example 11 The operations described in Example 3 are repeated, adding thereto the only next change densification . discontinuously for 2 hours.
The dried product has the following characteristics - carbonate content (by weight) = 60.8%, - silicate content (by weight) = 19.3% t 0.5%, - water content (by weight) = 19.9 unfilled filling density = 0; 91 g / cm3 -% by weight of refusal at 1 mm = 1.6%, - median diameter = 0.57 mm -% by weight from 0.2 mm = 1.22%
- 90% (by weight) of the product dissolves in 37 s (aqueous solution to 35 g / 1 at 20 ° C), - 95% (by weight) of the product dissolves in 45 s (aqueous solution to 35 g / 1 at 20 ° C), The granules exhibit excellent storage behavior.
I0 Examples 12 and 13 the "builder" performances of the cogranules of example 8 are measured according to the method described in examples 1 to 5.
They are compared to those of a mixture of carbonate powder sodium and atomized sodium silicate powder ratio Si02 / Na20 = 2 containing 22% water in the finished product (i.e. 28.2%
of water compared to dry silicate) in a 3/1 weight ratio (atomized carbonate / R2).
The results are shown in Table III.
The amounts of carbonate and silicate shown in this table are expressed in sec.
It can be seen that the performance of the cogranules is better than those of a mixture of powders having the same ratio silicate / carbonate.
Example 14 We prepare in a LODIGE M5G ~ mixer, according to the operating mode examples 6 and 7, particles from - 1800 g of light powdered sodium carbonate, with a average diameter of the order of 110 μm - 1200 g of sodium silicate solution of molar ratio Si02 / Na20 = 3.4 to 37% of dry extract.
After 5 minutes of adding the silicate solution, 5 minutes additional mixing and stay in the open air for 2 hours at the room temperature, we recover a product whose characteristics : 35 are as follows:
- sodium carbonate: 60% by weight - silicate = 20% by weight water associated with silicate - 20% by weight (i.e. 100 ~ per compared to dry silicate) ~ "" ~

- average diameter = 400 µm This product is introduced by dry mixing with additives to to obtain the following composition for washing machine Composition of detergent parts by weight . linear alkylbenzene sulfonate 25 . CEMULSOL DB 618 ~ 3 . CEMULSOL LA 90 ~ 2 (SFOS surfactants) . zeolite 4A 18 . product of example 14 25.8 -. SOKALAN CP5 ~ 4 (BASF copolymer) . carboxymethylcellulose 1.5 . TINOPAL DMSX 0.2 . TIMOPAL SOP 0.2 (CIBA-GEIGY brighteners) 2p. ESPERASE ~ (NOVO enzyme) 0.3 . RHODORSIL 20444 ~ 2 (RHONE-POULENC anti-foam) . Na perborate, 4H20. 15 . TAED 3 2 ~

pH (lOg / 1) = 10.25 The dirt removal performance test is performed in a washing machine FOM 71 ~ from WASCATOR.

30 The test conditions are as follows ., - cycle used: 60C

- total cycle time: 70 minutes; no prlavag e - number of cycles: 3 per detergent 35 - water hardness: 32 degrees French hydrotim - load of linen: 3.5 kg of white cotton tea towels - test fabrics. by washing, we introduce, by pinging them on tea towels, two next series of fabrics Test-Fabri c ~ p 5 bb 7 4 Gray cotton Krefeld 10 C

Polyester / gray cotton: Test-Fabric Krefeld 20 C

Protein stains: Blood (EMPA 111) Cocoa (EMPA 112) Mixed (EMPA 116) Oxidizable stains: Tea (Krefeld 10 G) Unbleached cotton (EMPA 222) Wine (EMPA 114) - Doses of detergents 1st series: 5 g / 1, i.e. 5 x 20 = 100 g per wash 2nd series: 8 g / 1, i.e. 8 x 20 = 160 g per wash Method for measuring the removal of dirt and stains Photometric measurements (measurements of the amount of light reflected by the fabric) used to calculate the percentages soil removal. We use the ELREPHO 2000 device from DATACALOR.
The removal of soiling is expressed by the formula CB
Elimination in% _ ----- X 100 AB
where A = reflectance of the blank control sample B = reflectance of the soiled control sample C = reflectance of the soiled sample after washing 2p56674 The reflectances are determined using the component trichromatic blue, without the action of optical brighteners.
Number of measurements made per sample = 4 5 Number of samples per wash - 2 Number of washes = 3 Or 4 X 2 X 3 - 24 measurements by soiling, by product and by concentration studied.
The washing machine anti-encrustation performance test is made in a SCHULTESS SUPER 6 D ~ LUXE drum machine The test conditions are as follows - cycle used: 60 ° C
- total cycle time = 65 minutes; no prewash - number of cycles: 25 cumulative washes - water hardness: 21.2 French hydrotimetric degrees - test fabric used: control strip responding exactly to specifications developed in standard NFT 73.600 - laundry load: 3 kg of 100% cotton terry towels - detergent doses: 5 g / 1 The test pieces which have undergone 25 washes are dried: they are weighed and calcines at 900 ° C.
The% of weight of ash is measured relative to the weight of starting test tubes.
The results of the various tests are shown in Table IV.
Example 15 A detergent similar to that of Example 14 is prepared by replacing the builder mix zeolite 4A + product of example 14 + SOKALAN CP5 by the following "builder" mixture . zeolite 4A 30 parts . silicate R2 atomized 3 light carbonate 6 . sodium sulfate 4.8 2 ~ ~ ~ 6 . SOKALAN CP5 4 Soil removal test results and anti-scaling agents are listed in Table IV.
Examples 16-18 The product of Example 8 is introduced by mixing into a LODIGE
M5G ~~ to additives to obtain compositions for dishwashers.
1.0 These compositions appear in Table V.
These compositions are tested in a household dishwasher MIELE ~
whose water softener is not regenerated; therefore it delivers a hard water with a total hardness of 30 ° TH French.
With each composition used at 3 g / liter of water, we proceed to ll5 10 cumulative washes of soda-lime glass plates, at the start perfectly clean.
The plates are then subjected to a photometric measurement at using a GARDNER device, identical to that used in Examples 1 to 5.
.? 0 We measure the total amount of light L returned by the sample.
When L is between 4 and 7, we consider the result as very good, the glass is crystal clear.
When L is between 7 and 14, a slight haze is visible.
The product of Example 8 is compared in a fairly formulation close to a mixture of sodium carbonate cogranules and cogranules of BRITSIL H20 ~ (of Si02 ~ Na20 = 2 ratio and containing 20 of water - sold by Philadelphia Quartz).
The results are shown in Table V.
30 It can be seen that the use of cogranules from Example 8 makes it possible to decrease the amount of sodium citrate (expensive) and polyacrylate (not biodegradable).

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Claims (36)

1. A builder agent, characterized in that it is obtained by adsorption and / or absorption by contacting a concentrated aqueous solution of a metal silicate alkaline with SiO2 / M2O molar ratio of the order of 1.6 to 3.5 and having a dry extract of the order of 10 to 60% containing at minus 30% of silicon in Q2 and Q3 form with a inert inorganic support with respect to silicate, said silicate support being different from sodium tripolyphosphate and being present in quantity such as the amount of water remaining associated with said silicate after adsorption and / or absorption corresponds to a silicate weight ratio expressed in dry / water associated with silicate of the order of 100/120 to 100/40, where M is an alkali metal, the form Q2 signifying that each atom of silicon participates in two -Si-O-Si- bonds, both remaining links being a termination -Si-OX where X is a alkali metal or H, and the form Q3 meaning that each atom of silicon participates in three bonds -Si-O-Si-, the bond remaining being a -Si-OX termination. 2. Agent according to claim 1, characterized in what support is chosen from metal carbonates alkali, sodium sulfate, sodium borate, sodium perborate, sodium metasilicate, phosphates and mixtures of two or more of these salts. 3. Agent according to claim 2, characterized in what the metal carbonates are sodium carbonate. 4. Agent according to claim 2 or 3, characterized in that said support is a phosphate trisodium. 5. Agent according to claim 2 or 3, characterized in that said support is carbonate of sodium. 6. Agent according to any one of the claims 1 to 4, characterized in that the contacting operation is carried out by spraying said concentrated solution silicate on the. support in particulate form at a temperature of the order of 20A to 95A. 7. Agent according to claim 5, characterized in what the contacting operation is done by spraying said concentrated silicate solution on the support in particulate form at a temperature of in the range of 20 to 95 ° C. 8. Agent according to any one of the claims 1 to 5 and 7, characterized in that the support represents 55 at 95% of the weight of the supported solution expressed in sec. 9. Agent according to claim 6, characterized in what the support represents from 55 to 95% of the weight of the supported solution expressed in sec. 10. Agent according to any one of the claims 1 to 5, 7 and 9, characterized in that it is in the form of spherical cogranules of hydrated metal silicates alkali and alkali metal carbonates. 11. Agent according to claim 8, characterized in what it comes in the form of spherical cogranules of hydrated alkali metal silicates and carbonates of alkali metals. 12. Use of the agent described in one any of claims 1 to 5, 7, 9 and 11, in a detergent composition as an agent builder. 13. Use of the agent described in claim 8, in a detergent composition as that agent builder. 14. Spherical cogranulate of hydrated silicates alkali metals and alkali metal carbonate, characterized in that it is obtained by the process comprising the following steps:
- spraying at a temperature of around 20 at 95 ° C an aqueous solution based on metal silicates alkalis containing at least 30% silicon atoms in form Q2 and Q3 or based on a mixture of said silicates and of alkali metal carbonates and having a rate dry extract of the order of 30 to 55% by weight, said silicate of alkali metal with a SiO2 / M2O molar ratio, where M is an alkali metal, on the order of 1.6 to 3.5, on a bed rolling of particles based on alkali metal carbonates running in a rotary granulation device, at a temperature from 15 to 120 ° C, the speed of the particles, the thickness of the moving bed and the flow of the sprayed solution being such that each particle is transforms into a plastic co-granule upon contact with other particles;
- the cogranules obtained are subjected to an operation densification; and - said densified cogranules are dried, up to obtain a water content associated with the corresponding silicate a silicate weight ratio expressed in dry / water associated with silicate of the order of 100/120 to 100/40;
the form Q2 meaning that each silicon atom participates with two bonds -Si-O-Si-, the two remaining bonds being a termination -Si-OX where X is an alkali metal or H; and the form Q3 meaning that each silicon atom participates in three -Si-O-Si- bonds, the remaining bond being a -Si-OX termination. 15. Co-granulated according to claim 14, character-laughed at in that the particles making up the moving bed are based on an alkali metal carbonate having:
- an average diameter of the order of 10 to 150 10-6 m;
- an unfilled filling density of the order from 0.4 to 1.1 g / cm3;
- a water content of the order of 0.05 to 0.4%; and - a rate of insoluble matter of the order of 5 to 100 mg / kg. 16. Co-granulated according to claim 14 or 15, characterized in that the particles constituting the bed containing less than 10% of the weight of the co-granules of minus a particulate detergent additive of a different nature than an alkali metal carbonate and having a diameter and a density close to that of the carbonate particles of alkali metal. 17. Co-granulated according to claim 14 or 15, characterized in that the granulating device is a rotary granulator allowing thin layer scrolling particles. 18. Cogranulate according to claim 16, character-laughed in that the granulating device is a granulator rotary allowing the thin layer scrolling of particles. 19. Cogranulate according to claim 17, character-laughed in that the rotary granulator is a bezel. 20. Co-granulated according to any one of the claims cations 14, 15 and 18, characterized in that the device for granulation is a rotary drum. 21. Co-granulated according to claim 16, characterized in that the granulating device is a rotating drum. 22. Co-granulated according to any one of the claims cations 14, 15, 18, 19 and 21, characterized in that the quantities of silicate solution or mixture silicate / carbonate to be sprayed and particles based on carbonate to be used correspond to a flow ratio of liquid / particle flow ranging from 0.2 to 0.8 l / kg, these values being expressed as sodium salts. 23. Cogranulate according to claim 20, character-laughed at that the amounts of silicate-based solution or of a silicate / carbonate mixture to be sprayed and of particles based on carbonate to be used correspond to a liquid flow / particle flow ratio ranging from 0.2 at 0.8 l / kg, these values being expressed as sodium salts. 24. Co-granulated according to any one of the claims cations 14, 15, 18, 21 and 23, characterized in that the densification operation is carried out at temperature ambient by rolling the cogranules obtained in the granulation in a rotary device. 25. Cogranulate according to claim 22, character-laughed in that the densification operation is carried out at ambient temperature by rolling the cogranules obtained at the granulation step in a rotary device. 26. Cogranulate according to claim 24, character-laughed at in that the densification operation is carried out in a rotating drum. 27. Co-granulated according to any one of the claims tions 14, 15, 18, 19, 21, 22, 25 and 26, characterized in that the cogranulate obtained after densification is dried in a bed fluidized. 28. Co-granulated according to claim 24, charac-terized in that the cogranulate obtained after densification is dried in a fluidized bed. 29. Co-granulated according to any one of the claims cations 14, 15, 18, 19, 21, 23, 25, 26 and 28, characterized in that the cogranulate obtained after drying is added, by spraying, small amounts of liquid compounds acceptable in the detergency field. 30. Co-granulated according to claim 27, character-laughed in that the cogranulate obtained after drying is added, by spraying, small amounts of acceptable liquid compounds in the field of detergency. 31. Spherical co-granulate based on silicates alkali metal hydrates containing at least 30% atoms of silicon in the form Q2 and Q3, where Q2 means that each silicon atom participates in two bonds -Si-O-Si-, both remaining links being a termination -Si-OX where X is a alkali metal or H and Q3 means that each silicon atom participates in three -Si-O-Si- bonds, the remaining bond being a termination -Si-OX and metal carbonates alkaline, characterized in that they have:
- a silicate content of SiO2 / M2O molar ratio from 1.6 to 3.5, of the order of 8 to 38% by weight where M is a metal alkaline;
- a carbonate content of the order of 47 to 87% by weight;
- a water content of the order of 5 to 25% by weight;
- an unfilled filling density of the order from 0.7 to 1.5 g / cm3; and - a median diameter of the order of 0.4 to 1.8 mm, with a log10 standard deviation of 0.02 to 0.3;
the silicate weight ratio expressed in dry / remaining water associated with silicate ranging from 100/120 to 100/40. 32. Spherical silicate cogranulate hydrated sodium containing at least 30% silicon atoms in the form Q2 and Q3, where Q2 means that each silicon atom participates in two -Si-O-Si bonds; the two bonds remaining being a termination -Si-OX where X is a metal alkaline or H and Q3 means that each silicon atom participates in three -Si-O-Si- bonds, the remaining bond being a termination -Si-OX, and of sodium carbonate, characterized in that they have:
- a silicate content of molar ratio SiO2 / Na2O from 1.8 to 2.6, of the order of 24 to 31% by weight;
- a carbonate content of the order of 64 to 69% by weight;
- a water content of 12 to 20% by weight;
- an unfilled filling density of the order from 0.7 to 1.5 g / cm3, - a median diameter of the order of 0.4 to 0.8 mm, with a log10 standard deviation of 0.05 to 0.1;
- a dissolution rate of 90% in water less than 2 minutes and less than 95 minutes less than 95 minutes;
the silicate weight ratio expressed in dry / remaining water associated with silicate ranging from 100/120 to 100/40. 33. Co-granulated according to claim 32, characterized in that the non-packed filling density is on the order of 0.8 to 1 g / cm3. 34.- Detergent composition, characterized in that that it comprises co-granules defined according to any one of claims 14, 15, 18, 19, 21, 23, 25, 26, 28, 30, 31, 32 and 33. 35. Composition according to claim 34, character-laughed at in that the detergent composition is a composition detergent powder for dishwashing machine which includes co-granules as defined according to one any of claims 14, 15, 18, 19, 21, 23, 25, 26, 28, 30, 31, 32 and 33 at a rate of 3 to 90% by weight of silicate dry relative to the total weight of the composition. 36. Composition according to claim 34, characterized in that the detergent composition is a powder detergent composition for washing machine which comprises cogranules as defined according to any one of claims 14, 15, 18, 19, 21, 23, 25, 26, 28, 30, 31, 32 and 33 at a rate of 3 to 60% by weight of dry silicate relative to the total weight of the composition.