FR2721317A1 - Detergent builder comprising co-polymer formed by condensation polymerisation - Google Patents

Abstract

The silicated polymeric detergent builder is a copolymer obtd. by condensation polymerisation of (A) an alkali metal silicate with molar ratio SiO2/M2O of 0.5-4 (1.2-3.5), and (B) an organo-Si cpd. comprising (a) a polyorganosiloxane with units of formula RaYbSiO(4-(a+b))/2, or (b) an alkali metal organosiliconate of formula RnSi(OM)p()OH)4-(n+p) and/or its condensation derivs., and/or (c) an organosilane of formula RnSiX4-n. a = at least 1; b = 0 or 1; a + b = 1-3; R = 1-20 C (1-18 C) hydrocarbon gp., opt. halogenated and opt. with N or O atoms); Y = OH; M = NH4 or alkali metal (pref.); n = 103; p = at least 1; n + p = not above 4; X = 1-20 C alkoxyl, OH or halogen.

Description

 The present invention relates to a new family of products derived from silicates, which have builder and surfactant properties.

 The use of various silicon compounds is well known in detergency, the most commonly used compounds being alkali metal silicates.

 Silicates are conventionally known to be alkaline agents, to be corrosion inhibitors, to capture in complex form the ionic magnesium supplied by calcareous waters. They are also used for a certain dispersing power, but they are only additions to complex builders systems which conventionally comprise mineral or organic sequestering agents, exchangers such as zeolites, organic polymers, alkaline precipitants such as sodium carbonate, etc. They play therefore in their traditional form only a minor role of adjuvant detergency.

 They are also recognized as agglomeration and structural agents; they play this role in particular when they are present in the suspensions or slurries before atomization, or when they are used as binding agents in the granulation processes of the compositions.

 Different forms of silicates have been developed which give these compounds improved properties. In particular, silicates are increasingly used in the form of solid products which are introduced into post-additive powder detergent compositions after the atomization tower. These products are of practical use for the preparation of the final mixtures and they are especially recommended in the case of zeolite-based formulas to avoid the problems of incompatibility between zeolite and silicate during the drying of a suspension containing these compounds.

 These solid products are obtained by separate atomization of the silicate solution, then optionally are then modified by granulation or compaction, so as to increase their average diameter and reduce their tendency to dusting and caking in a humid atmosphere.

 This type of product is still used conventionally in low doses and simply as an addition to conventional builders' systems, usually based on zeolite as the main builder. They do not possess any particular properties distinguishing them from traditional silicates.

More recently, a different form of alkali silicate has been proposed as a detergency builder, with improved calcium and magnesium exchange properties of calcareous waters and having higher dispersancy. This product is a hydrated silicate, more particularly this silicate can be supported by sodium carbonate and thus be in the form of cogranules. Such products are described in particular in applications EP-A-0 488 868 and EP
AO 561 656.

 The object of the invention is to propose novel products derived from silicates that can be used in detergency, which exhibit both builders and surfactant properties.

For this purpose, the subject of the invention is a product obtained by condensation reaction between (A) an alkali metal silicate, the alkali metal being chosen from sodium, potassium and lithium, and (B) at least one compound organic silicon selected from - a silicone compound comprising patterns of the type
RaYbSiO [4-a-if b is 0 or 1, (a + b) is 1 to 3,
R represents a hydrocarbon group and Y a nonionic hydrocarbon functional group containing at least one heteroatom such as nitrogen or oxygen, an alkali metal siliconate of formula
RnSi (OM) p (OH) 3 (npZet / or the condensation products which
derive from it, where
R has the previous meaning,
n is 1 to 3,
M represents an alkali metal selected from sodium,
potassium and lithium,
p is greater than or equal to 1,
(n + p) is less than or equal to 4, and - a silane of formula
RnsiX4-n Where
R and n have the above meanings,
X represents a C1-C20 alkoxyl group or a group
hydroxyl or a halogen atom.

 In these different formulas, the groups R, which are identical or different, are chosen from a linear or branched, optionally halogenated alkyl radical, a cycloalkyl radical, an aryl radical such as the phenyl and naphthyl radical, an arylalkyl or alkylaryl radical or an alkenyl radical. such as the vinyl or allyl radical, an alkynyl radical such as the ethynyl or propynyl radical.

 In the above silicone compound formula, the Y group is analogous to the R group and has one or more functionalities which may especially be hydroxy, ether, carbonyl, ester, amine or amide functions.

 Preferably, the compound (A) is an alkali metal silicate of molar ratio SiO 2 / M'2 O, where M 'is the alkali metal, of between 0.5 and 4, the metal M' being still more preferably sodium.

 In the compounds (B), the saturated or unsaturated group R can be linear or non-linear and has from 1 to 20 carbon atoms.

 Examples of alkyl radicals R include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl radicals; examples of R cycloalkyl radicals include cyclopentyl, cyclohexyl and cycloheptyl radicals; examples of R arylalkyl radicals include benzyl and phenylethyl radicals; examples of R alkylaryl radicals include tolyl and xylyl radicals.

A preferred R group is methyl.

Among the compounds (B) which may lead to the products according to the invention, mention may be made of siliconates, such as sodium methylsiliconate CH3
If (ONa) 3 or potassium CH3-Si (OK) 3, alkoxysilanes such as methyltriethoxysilane CH3-Si (OEt) 3, octyltrimethoxysilane C, H ,, - Si (OMe), or octyltriethoxysilane CaH1, - If (OEt) 3, but also silicones, such as hexamethyldisiloxane (CH 3) 3 Si-O-Si (CH 3) 3, or resins or silicone oils of variable molecular mass comprising at least one -Si (CH 3) unit 20-.

 The reaction leading to the product of the invention can be carried out by bringing into contact the compounds (A) and (B). The silicate (A) may be in the form of an aqueous solution advantageously containing from 5 to 55% of dry matter or in the form of an amorphous or crystalline powdery or granular solid advantageously containing from 0.5 to 50% of water.

 The compound (B) is preferably used, according to its solubility in water, in the form of aqueous solution or emulsion, or microemulsion, aqueous.

For example, potassium methylsiliconate has the property of being soluble in water in significant proportions, ie about 50%. On the other hand, other products with fewer Si-OH bonds or
Si-OM that methylsiliconate, which is particularly the case of high molecular weight silicone products, may be used in emulsion or microemulsion in water.

 Another possibility for the compound (B) to be in a form that is sufficiently reactive is to carry out a hydrolysis of the compound (B) with the alkali silicate (A), preferably at more than 50 ° C. The hydrolysis leads to molecules smaller ones that can react with silicate via newly formed terminal SiO units.

 Depending on the case, the reaction mixture may be a liquid mixture (A) / liquid (B) or a liquid mixture (B) / powder (A).

 The compounds (A) and (B) can be mixed in very large proportions. Advantageously, 10 to 99.9 parts of (A) are used for 90 to 0.1 parts of (B), expressed in dry weight.

 Preferably, the reaction mixture comprises at least 40% of compound (A) relative to the dry weight of the mixture (A) + (B).

 During said copolymerization of the compounds (A) and (B), -Si-O-Si- groups are formed, in which one silicon atom comes from the compound (A) and the other compound (B), with a starting point of a molecule of water, MOH base or ROH alcohol.

 The resulting mixture can be analyzed by 29Si NMR. Silicon NMR makes it possible to measure the number of Si atoms close to the Si atoms originating from the compound (A) and the Si atoms from the compound (B), and makes it possible to specify the environment of the Si-R sites of the compound (B). Thus, it is shown by NMR that the mixture of the compound (A) and the compound (B) results in the formation of new molecules consisting in part of R'n-SiO4n sites, with n = 1 to 3 and R 'identical or different and R '= R or X, and Six4 sites.

 Depending on the nature of the starting products (A) and (B), the copolymerization may or may not be spontaneous, but in a limited way, depending on the physico-chemical conditions of implementation.

 The copolymerization can be triggered or increased, in particular - either by total or partial evaporation of the water of the mixture (copolymerization by elimination of water molecule) - or by modifying the pH of the mixture or its ionic strength in order to form Si groups -OH promoting the copolymerization (addition of base, acid or salt), - either by heating, at atmospheric pressure or higher, - or by simultaneously or successively at least two of these three operations.

 As said above, the copolymerization can be done spontaneously. For example, if a sodium silicate having an SiO 2 / Na 2 O molar ratio of 3.5 which has a pH of about 11.5 and potassium methylsiliconate having a pH of 13.5 is brought into contact, an intermediate copolymerization product resulting from the drop in pH of potassium methylsiliconate and the rise in pH of sodium silicate will be obtained. But, even in this case, it will be preferable to increase the copolymerization by one of the preceding operations.

 The product of the reaction can then be in liquid or solid form, according to the technique used to complete the copolymerization. The product is usable in both forms.

 However, since the detergent industry mainly requires solid forms for its raw materials, it is possible to transform the products obtained in liquid form into powder or granular form.

 Two shaping is preferred - drying, by an atomization technique or any other drying technique known to lead to a solid product.

 In the case of drying by spraying or in an oven, the product obtained is in powder form.

 In the case, for example, of static drying, a solid mass is obtained which can be ground to reduce it to powder.

 When the copolymerization is obtained by evaporation of water from the reaction mixture, the two copolymerization and solid forming steps can be carried out simultaneously in the same drying device.

- Absorption, on a mineral support, chemically inert vis-à-vis the copolymerization product, followed by drying by total or partial evaporation of the water present in the product.

 The inorganic support may be chosen from: sodium carbonate, sodium metasilicate, sodium borate, sodium perborate, phosphates or polyphosphates such as trisodium phosphate, sodium tripolyphosphate, ... these products being alone or mixed with each other. Products having a detergency activity and more particularly sodium carbonate are preferably used.

 Drying may be more moderate than the previous one because of the ability of the carrier to retain some of the water initially present in the solution.

 The invention also relates to such compositions comprising the copolymerization product of (A) and (B) in an absorbed form on a chemically inert inorganic support.

 It is advantageous that during the evaporation steps, the degree of dryness of the product of the invention as well as that of the composition obtained by absorption, are controlled and that the water content in the final product remains within the range of 1 to 40% of water relative to the dry product, preferably 5 to 30%.

 The invention also relates to a process for preparing a silicate derivative product by which the components (A) and (B) are reacted as previously described.

 It has been found that the products according to the invention, as well as the compositions comprising said products and a chemically inert mineral support, possess the known builders properties for silicates but they also exhibit an amphiphilic behavior which gives them interesting surface-active properties.

 Thus, they can be used in detergent compositions in order to replace all or part of the traditional builders, but also to replace some of the surfactants usually added to the builders.

 The invention therefore also relates to the use of said products and compositions comprising said absorbed products on a chemically inert mineral carrier, in detergent compositions, as well as the latter detergent compositions.

 The present invention will now be illustrated by the following examples.

EXAMPLES
In all the examples, the surface tension measurements were carried out using a LAUDAO apparatus.

Example 1
Several products according to the invention are prepared by reacting sodium silicate with potassium methylsiliconate in varying proportions.

 In a reactor, an aqueous silicate solution with an SiO 2 / Na 2 O molar ratio of 2 and 44.68% of solids is mixed with an aqueous solution of potassium methylsiliconate containing 45.12% solids, sold by Rhone-Poulenc under the name RHODORSIL 51 T9, in proportions indicated in Table 1.

 The mixture being homogeneous, the water of the reaction mixture is partially evaporated by drying in an oven at 105 ° C. for 48 hours. A solid is obtained which is then ground.

 A powder product is then obtained. This powder dissolves easily in water.

 A test is carried out before the drying step to check that there has been a copolymerization of the two starting materials by applying the silicon NMR to the homogeneous mixture. The degree of copolymerization measured corresponds to the ratio of the number of silicon atoms from the siliconate bonded to silicon atoms from the silicate to the total number of siliconate silicon atoms. The results corresponding to each mixture are reported in Table 1.

 The subsequent drying step increases the degree of copolymerization with respect to these values.

TABLE 1

<tb> Mass <SEP> of <SEP> silicate <SEP> Mass <SEP> of <SEP> silico- <SEP> Rate <SEP> of <SEP> copolymer
<tb><SEP> (g) <SEP> nate <SEP> (g) <SEP> rization <SEP> (%)
<tb><SEP> O <SEP> 100 <SEP><SEP> o <SEP>
<tb><SEP> 20 <SEP> 80 <SEP> 23.87
<tb><SEP> 40 <SEP> 60 <SEP> 40.53
<tb><SEP> 50 <SEP> 50 <SEP> 39.78
<tb><SEP> 60 <SEP> 40 <SEP> 43.64
<tb><SEP> 80 <SEP> 20 <SEP> 47.6
<tb><SEP> 90 <SEP> 10 <SEP> 51.38
<Tb>
Other products according to the invention are prepared under the same conditions with the same reagents in different proportions indicated in Table 2. The powder obtained after drying is dissolved in water at different concentrations and the surface tension of the solutions thus prepared. The measured values make it possible to evaluate the surfactant properties of the products. The results are shown in Table 2.

TABLE 2

<tb> Mass <SEP> of <SEP> if <SEP> Mass <SEP> of <SEP> if <SEP> Concentration <SEP> Voltage <SEP>
<tb><SEP> licate <SEP> liconate <SEP> (g) <SEP> in <SEP> perfected water <SEP>
<tb><SEP> (g) <SEP> of the <SEP> product <SEP> (10 ~ 5N / cm) <SEP>
<tb><SEP> got <SEP> after
<tb><SEP> drying
<tb><SEP> (g / l)
<tb><SEP> 95 <SEP> 5 <SEP> 0.981 <SEP> 66.1
<tb><SEP> 95 <SEP> 5 <SEP> 2,394 <SEP> 52,4
<tb><SEP> 99 <SEP> 1 <SEP> 1,155 <SEP> 55,4
<tb><SEP> 99 <SEP> 1 <SEP> 2.572 <SEP> 45.4
<Tb>
The surface tension of the pure water is 70.6 × 105 N / cm. A lowering of the surface tension of the water is thus observed in the presence of the silicate and siliconate copolymer.

Example 2
Products according to the invention are prepared by reaction of sodium silicate with octamethyltetracyclosilane, in variable proportions.

 In a reactor, an aqueous silicate solution with an SiO 2 / Na 2 O molar ratio equal to 2 and 44.68% solids is mixed with octamethyltetracycloilane, marketed by Rhone-Poulenc under the name SILOX D4X, in proportions shown in Table 3.

 The mixture being homogeneous, the water of the reaction mixture is partially evaporated by drying in an oven at 105 ° C. for 7 days. A solid is obtained which is then ground.

 A powder product is then obtained. This powder dissolves easily in water.

 A test is carried out after the drying step to evaluate the surfactant properties of the product for different proportions of silicate and silane, by measurement of surface tension. The results of the measurements are shown in Table 3.

TABLE 3

<tb> Mass <SEP> of <SEP> if <SEP> Mass <SEP> of <SEP> if <SEP> Concentration <SEP> Voltage <SEP>
<tb><SEP> licate <SEP> (g) <SEP> I <SEP><SEP> lane <SEP> (g) <SEP> in <SEP> water <SEP> from <SEP> I <SEP > perfective
<tb><SEP> product <SEP> obtains <SEP> (10-5N / cm) <SEP>
<tb><SEP> nu <SEP> after <SEP> se
<tb><SEP> chage <SEP> (g / l)
<tb><SEP> 100 <SEP> - <SEP><SEP> 0.5 <SEP> 0.928 <SEP> 69.6
<tb><SEP> 100 <SEP> 0.5 <SEP> 2,259 <SEQ> 54.9
<tb><SEP> 100 <SEP> 1 <SEP> 2,448 <SEP> 57,9
<tb><SEP> 100 <SEP> 2 <SEP> 1,053 <SEP> 64.3
<tb><SEP> 100 <SEP> 2 <SEP> 1,975 <SEP> 55.5
<tb><SEP> 100 <SEP> 5 <SEP> 1.252 <SEP> 67.2
<tb><SEP> 100 <SEP> 5 <SEP> 2,411 <SEP> 55.4
<tb><SEP> 100 <SEP> 10 <SEP> 1.281 <SEP> 68.5
<tb><SEP> 100 <SEP> 10 <SEP> 2,232 <SEP> 57
<Tb>
The surface tension of the water is lowered in the presence of the silicate / silane copolymer with respect to the surface tension of the pure water (70.6 × 10 -5 N / cm).

 On the other hand, the water content in the hour. The difference in weight of the product before and after calcination represents the weight of water and organic matter contained in this product. The weight of the water in the product is deduced by subtracting the weight of the known organic matter.

The results are gathered for the different products in the following table 4
TABLE 4

<tb> Mass <SEP> of <SEP> silicate <SEP> Mass <SEP> of <SEP> silane <SEP>% water <SEP> in <SEP> weight
<tb><SEP> (g) <SEP> (g)
<tb><SEP> 100 <SEP> 0.5 <SEP> 22.18
<tb><SEP> 100 <SEP> 1 <SEP> 20.93
<tb><SEP> 100 <SEP> 2 <SEP> 20.17
<tb><SEP> 100 <SEP> 5 <SEP> 18.14
<tb><SEP> 100 <SEP> 10 <SEP> 19.65
<Tb>
Example 3
Example 2 is repeated with instead of
SILOX D4X, a silicone oil marketed by Rhône
General pattern poulenc

 The same test as that of Example 1 carried out after the drying step is carried out to evaluate the surfactant properties of the product for different proportions of silicate and silicone. The results are shown in Table 5.

proportions of silicate and silicone. The results are shown in Table 5.

TABLE 5

<tb> Mass <SEP> of <SEP> if <SEP> Mass <SEP> of <SEP> Concentration <SEP> Tension <SEP> su
<tb><SEP> licate <SEP> (g) <SEP> silicone <SEP> (g) <SEP> in <SEP> water <SEP> of <SEP> perfective
<tb><SEP> product <SEP> obtains <SEP> (lO5N / cm) <SEP>
<tb><SEP> nu <SEP> after <SEP> se
<tb><SEP> chage
<tb><SEP> (g / l)
<tb><SEP> 100 <SEP> 0.5 <SEP> 1.292 <SEP> 68.8
<tb><SEP> 100 <SEP> 0.5 <SEP> 2.29 <SE> 57.7
<tb><SEP> 100 <SEP> 1 <SEP> 2.088 <SEP> 68.2
<Tb>
II
The surface tension of the water is lowered in the presence of the silicate / silicone oil copolymer with respect to the surface tension of the pure water (70.6 × 10 -5 N / cm).

 The water content in the final product was also measured as in Example 2.

The results are gathered for the different products in the following table 6
TABLE 6

<tb> Mass <SEP> of <SEP> silicate <SEP> Mass <SEP> of <SEP> silicone <SEP>% water <SEP> in <SEP> weight
<tb><SEP> (g) <SEP> (g)
<tb><SEP> 100 <SEP> 0.5 <SEP> 16.95
<tb><SEP> 100 <SEP> 1 <SEP> 18.47
<Tb>
Example 4
Example 2 is repeated, using instead of SILOX D4t, methyltriethoxysilane (MTEOS) of formula: MeSi (OEt) 3
The same test as that of Example 1 carried out after the drying step is carried out in order to evaluate the surfactant properties of the product for different proportions of silicate and silane. The results are shown in Table 7.

TABLE 7

<tb> Mass <SEP> of <SEP> if <SEP> Mass <SEP> of <SEP> Concentration <SEP> Tension <SEP> su
<tb><SEP> licate <SEP> (g) <SEP> MTEOS <SEP> (g) <SEP> in <SEP> water <SEP> of perfected <SEP>
<tb><SEP> product <SEP> obtains <SEP> (10-5N / cm) <SEP>
<tb><SEP> nu <SEP> after <SEP> se
<tb><SEP> chage <SEP> (g / l)
<tb><SEP> 100 <SEP> l <SEP> 0.934 <SEP> 63.5
<tb><SEP> 100 <SEP> 1 <SEP> 2,414 <SEP> 48
<tb><SEP> 100 <SEP> 2 <SEP> 0.993 <SEP> 64.7
<tb><SEP> 100 <SEP> 2 <SEP> 2.075 <SEP> 53.8
<tb><SEP> 100 <SEP> 3 <SEP> 0.906 <SEP> 65.2
<tb><SEP> 100 <SEP> 3 <SEP> 2.039 <SEP> 51
<tb><SEP> 100 <SEP> 5 <SEP> 0.953 <SEP> 62
<tb><SEP> 100 <SEP> 5 <SEP> 2,166 <SEP> 60,4
<Tb>
The surface tension of the water is lowered in the presence of the silicate copolymer and MTEOS, relative to the surface tension of the pure water (70.6 × 10 -5 N / cm).

Example 5
Example 2 is repeated using octyltriethoxysilane (OTEOS) of formula: (EtO) 3SiC8Hl, instead of SILOX D4.

 The same test carried out after the drying step as in Example 1 is carried out to evaluate the surfactant properties of the product. The results are shown in Table 8 below.

TABLE 8

<tb> Mass <SEP> of <SEP> si- <SEP> Mass <SEP> of OTEOS <SEP> Concentration <SEP> Tension <SEP> su
<tb><SEP> licate <SEP> (g) <SEP> in <SEP> water <SEP> of perfected <SEP>
<tb><SEP> (g) <SEP> product <SEP> obtains <SEP> (10-SN / cm) <SEP>
<tb><SEP> nu <SEP> after <SEP> se
<tb><SEP> chage <SEP> (g / l)
<tb><SEP> 100 <SEP> 0.5 <SEP> 0.922 <SEP> 55.7
<tb><SEP> 100 <SEP> 0.5 <SEP> 2,637 <SEP> 45,5
<Tb>
A lowering of the surface tension of the water in the presence of the silicate copolymer and OTEOS is observed, with respect to the surface tension of the pure water (70.6 × 10 -5 N / cm),

Claims (18)

 1. Product obtained by condensation reaction between (A) an alkali metal silicate, the alkali metal being selected from sodium, potassium and lithium, and (B) at least one organic silicon compound selected from: - a compound silicone comprising patterns of the type RaYbSiOe4 (4 - (a - b). X represents a C1-C20 alkoxy group or a hydroxy group or a halogen atom. R and n have the above meanings, M represents an alkali metal selected from sodium, potassium and lithium, p is greater than or equal to 1, and (n + p) is less than or equal to 4, and - a silane of formula RnsiX4-n Where R has the above meaning, n varies from 1 to 3, R represents a hydrocarbon group and Y represents a nonionic hydrocarbon functional group containing at least one heteroatom such as nitrogen or oxygen; an alkali metal siliconate of formula RnSi (OM) p (OH) 4 nop; and or the condensation products derived from it, where where b is 0 or 1, (a + b) is 1 to 3,  2. Product according to claim 1, characterized in that it is obtained from an alkali metal silicate (A) of molar ratio SiO2 / M'20, where M 'represents the alkali metal, between 0.5 and 4.  3. Product according to claim 1 or 2, characterized in that it is obtained from a compound or a mixture of compounds (B) wherein R represents the methyl group.  4. Product according to any one of claims 1 to 3, characterized in that it is obtained by mixing an aqueous solution of alkali metal silicate (A) and a solution, an emulsion or an aqueous microemulsion of compound (B).  5. Product according to any one of claims 1 to 3, characterized in that it is obtained by mixing a compound (A) in the form of a powdery or granular solid, amorphous or crystalline and a solution, an emulsion. or an aqueous microemulsion of compound (B).  6. Product according to any one of claims 4 and 5, characterized in that the mixture comprises at least 40% by dry weight of compound (A) relative to the dry weight of the mixture (A) + (B).  7. Product according to any one of claims 4 to 6, characterized in that it is obtained by evaporation of water from the mixture (A) + (B), by changing the pH of the mixture or its ionic strength, by heating the mixture to a pressure greater than or equal to atmospheric pressure, or practicing simultaneously or successively at least two of these operations.  A composition comprising a product according to any one of claims 1 to 7 in an absorbed form on an inert mineral carrier.  9. Product according to any one of claims 4 to 8, characterized in that its degree of dryness is 1 to 40%, and preferably 5 to 30%, of water relative to the dry product.  10. A process for the preparation of a product according to claim 1, wherein (A) is an alkali metal silicate, the alkali metal being selected from sodium, potassium and lithium, and (B) at least one compound. organic silicon selected from: - a silicone compound comprising R a Y b SiO 2 type units where b is 0 or 1, (a + b) is from 1 to 3, R represents a hydrocarbon group and Y a nonionic hydrocarbon functional group containing at least one heteroatom such as nitrogen or oxygen, an alkali metal siliconate of formula RnSi (OM) p (OH) 4-np) and / or the condensation products derived from it, where R has the above meaning, n varies from 1 to 3, M represents an alkali metal selected from sodium, potassium and lithium, p is greater than or equal to 1, and (n + p) is less than or equal to 4, and - a silane of formula  RnsiX4-n WHERE R and n have the above meanings, X represents a C1-C20 alkoxyl group or a hydroxyl group or a halogen atom.  11. The method of claim 10 wherein an aqueous solution of alkali metal silicate (A) and an aqueous solution, emulsion or microemulsion of compound (B) are mixed.  12. The process according to claim 10, wherein a compound (A) is mixed in the form of an amorphous or crystalline powdery or granular solid and an aqueous solution, an emulsion or a microemulsion of compound (B).  13. The method of any one of claims 11 or 12, wherein the mixture comprises at least 40% by dry weight of compound (A) relative to the dry weight of the mixture (A) + (B).  14. A method according to any one of claims 11 to 13 whereby, in addition, evaporates all or part of the water of the mixture, the pH or the ionic strength of the mixture is modified, the mixture is heated to a higher pressure. or equal to the atmospheric pressure, or at least two of these operations are carried out sequentially or simultaneously.  15. Process for the preparation of a composition according to claim 8, wherein the product according to claim 1 in liquid form is absorbed on the inert inorganic support, then the mixture is subjected to total or partial evaporation.  16. A method according to any one of claims 10 to 15, wherein it is controlled that the degree of dryness of the product is 1 to 40%, and preferably 5 to 30%, of water relative to the dry product.  17. Use of a product or a composition according to one of claims 1 to 9 in a detergent composition, replacing all or part of the traditional builders and some of the surfactants traditionally used with builders.  18. A detergent composition containing a product or a composition according to one of claims 1 to 9, replacing all or part of the traditional builders and some of the surfactants traditionally used with the builders.