WO1996020268A1 - Non-corrosive, glass and tableware-protective alkaline agent and detergent composition containing same - Google Patents

Abstract

A non-corrosive, glass and tableware-protective alkaline agent, comprising at least one silicon polymer of a silicated organomineral copolymer obtained by the condensation polymerisation of an alkali metal silicate and an organic silicon compound selected from alkaline siliconates, condensates thereof, and alkoxysilanes. A detergent composition containing said alkaline agent is described, in particular for use in dish washers.

Description

 NON-CORROSIVE ALKALI AGENT FOR PROTECTING GLASS AND DISHWASHER AND DETERGENT COMPOSITION CONTAINING SAID ALKALI AGENT

The subject of the present invention is a non-corrosive alkaline protective agent for glass and tableware consisting of an organomineral silicate copolymer, its use in detergent compositions in particular for washing glass and tableware in a dishwasher, as well as detergent compositions based on said organomineral silicate copolymer, in particular for washing glass and dishes in a dishwasher.

Alkali metal silicates, in particular sodium silicates, are widely used in detergent compositions for dishwashers. They provide a buffering effect, detergent power and dispersing action in the detergent bath.

Metasiiates (SiO ₂ / M ₂ O ratio equal to 1 where M represents an alkali metal) have been particularly used in detergents for dishwashers because of their high detergent power. However, these high alkalinity products had the disadvantage of deteriorating the surface of the glass. Consequently, after a number of washes with this detergent, a frosted appearance of the glass, colored iridescence, white streaks or a continuous whitish veil appeared on the glass. They have been gradually replaced by disilicates (SiO ₂ / M ₂ O ratio equal to 2) which have the advantages of the alkaline silicates listed above. However, even if these disilicates have a lower alkalinity than metasiiates, they still do not sufficiently protect the glass against corrosion.

In certain compositions, the silicates have been replaced by sodium tripolyphosphate, which provides functions equivalent to silicates and which protects, in particular, glass against temporary deposits, particularly deposits of calcium carbonate. However, phosphates also have the disadvantage of causing corrosion of the glass. In fact, because of their calcium complexing power, they contribute to the surface rupture of the glass network by the passage of calcium in solution, which results in corrosion of the glass. In addition, phosphates are less and less used in detergents due to environmental standards.

The Applicant has found an alkaline agent for detergent compositions making it possible to reduce the degradation of glass and dishes which may occur during successive washes in a dish washing machine.

According to the invention, it is an alkaline protective agent for glass and tableware, characterized in that it consists of at least one silicon polymer based on an organomineral silicate copolymer capable of being obtained. by condensation polymerization - At least one ammonium or alkali metal silicate (A) of molar rap Siθ2 / M2θ of the order of 0.5 to 4, preferably of the order of 1, 2 to 3.5, t particularly from 1, 2 to 3.3, the symbol M representing an ammonium cation or preferably an alkali metal • and at least one organic silicon compound (B) chosen from

* alkaline siliconates of formula (I)

R _n Si (OM) _p (OH) 4. _n . _p (I) formula in which,

. R represents a hydrocarbon group, similar or different, containing from 1 to carbon atoms, preferably from 1 to 18 carbon atoms, optionally halogenated and optionally containing one or more nitrogen or oxygen heteroatoms. M represents an ammonium cation or preferably an alkali metal. (n + β) is less than or equal to 4, with n possibly ranging from 1 to 3 and β greater than or equal to

* the condensates of the siliconates of formula (I), soluble in ammonium silicate or of alkali metal (A) in aqueous solution

* the alkoxysilanes of formula (II)

R _n If (OR ') ₄ . _n (II) formula in which. R and n have the same definition as above. R 'represents a linear or branched alkyl group containing from 1 to 6 carbon atoms, preferably methyl or ethyl, the respective amounts of ammonium silicate or of alkali metal (A) and of organic silicon comp (B) corresponding to a mass ratio of Si from the organic comp / mass of total Si in the silicon polymer of the order of 0.0002 to minus 0.05, preferably of the order of 0.002 to 0.02, and very particularly of the order 0.003 to 0.006, said silicon polymer having a loss on ignition measured at 700 ° C. of the order of 1 30% by weight, preferably of the order of 18 to 28% by weight.

Among the ammonium or alkali metal silicates (A), mention may be made of ammonium, sodium, potassium, lithium, and very particularly those of sodium.

Among the symbols R of the different formulas of organic silicon compound (B), mention may be made of linear or branched alkyl radicals, such as methyl ethyl, propyl, butyl, hexyl, octyl, dodecyl, octadecyl ...; cycloalkyl radica, such as cyclopentyle, cyclohexyle, cycloheptyle ...; aryl radicals such as phenyl, naphthyl ...; arylalkyl or alkylaryl radicals, such as toly xylyl ...; alkenyl radicals, such as vinyl, allyl ...; polyalkylene polyamine alkyleneamine radicals (such as diethylene diamine, etc.), polyoxyalkylene, oxyalkylene, oxyalkylene and polyoxyalkylene radicals, etc. The preferred symbols R are linear or branched alkyl radicals containing from 1 to 12 carbon atoms, preferably from 1 to 8 carbon atoms, and very particularly methyl.

Among the organic silicon compounds (B) which can be used for the preparation of the silicon polymer, mention may be made of:

. sodium or potassium methylsiliconates of formula CH3 Si (ONa) 3 or CH3 Si (OIQ3, sodium or potassium propylsiliconates of formula C3H7 Si (ONa) 3 or C3H7 Si (OIO3, sodium or potassium butylsiliconates formula C4H9 Si (ONa) 3 or C4H9 Si (OIO3, sodium or potassium hexylsiliconates of formula C6H13 Si (ONa) 3 or C6H13 Si (OK) 3, sodium or potassium octylsiliconates of formula C8H17 Si (ONa) 3 or CgHi7 Si (OIO3, sodium or potassium dimethylsiliconates of formula (CH3) 2 Si (ONa) 2 or (CH3) 2 If (OK) 2, sodium or potassium methylpropylsiliconates of formula (CH3XC3H7) Si ( ONa) 2 or (CH3) (C3H7) If (OK) 2, the sodium or potassium methylbutylsiliconates of formula (CH3XC4H9) Si (ONa) 2 or (CH3) (C4Hg) If (OK) 2, the sodium methylhexylsiliconates or potassium of formula (CH3KC6H13) If (ONa> 2 or (CH3KC6H13) If (OK) 2, the sodium or potassium methyloctylsilicoπates of formula (CH ₃ ) (C8H ₁₇ ) Si (ONa) 2 or (CH ₃ ) .VS ₈ H ₁₇ ) If (OK) ... their mixtures and their condensates; . methyltrimethoxysilane of formula CH3 Si (OMe) 3, methyltriethoxysilane of formula CH3 Si (OEt) 3, octyltrimethoxysilane of formula C8H17 Si (OMe) 3, octyltriethoxysilane of formula C8H17 Si (OE 3, diethylenediaminetriethoxys formula ₂ N- (CH ₂ ) 2- H- (CH2) 2-Si (OEt) ₃ .... Dimethyldimethoxysilane of formula (01-13) 2 Si (OMe) 2, trimethylmethoxysilane of formula (CH3) 3 Si (OMe), dimethyldiethoxysilane of formula (CH3) 2 Si (OEt) 2, trimethylethoxysilane of formula (CH3) 3 Si (OEt) ...

The preferred siliconates of formula (I) are sodium or potassium methylsiliconates of formula CH3 Si (ONa) 3 or CH3 Si (OK) 3-

The condensates of the siliconates of formula (I) are considered to be soluble in said ammonium or alkali metal silicate (A) in aqueous solution, when their solubility is at least 50% by weight in an aqueous solution of silicate d ammonium or alkali metal (A) containing about 35 to 55% by weight of active material. Among the condensates of the siliconates of formula (I), mention may be made most particularly of commercial solutions of potassium methylsiliconate containing about 40 to 50% by weight of active material. The preferred alkoxysilanes of formula (II) are dimethyldimethoxysilane, trimethylmethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, and particularly methyl trimethoxysilane or methyl triethoxysilane.

Said silicon polymer based on organomineral silicate copolymer constituting the alkaline agent of the invention, can be obtained by polymerization of a monomeric compositi consisting of at least one alkali metal silicate (A) and at least alkali siliconate of formula (I) or at least one of its condensates; this polymerization operation can be carried out by bringing into contact with an aqueous solution of at least one alkali metal silicate (A) containing of the order of 35 to 55%, preferably of the order of 35 to 50% of its weight of active material, with at least one siliconate formula (I), preferably in aqueous solution containing of the order of 40 to 50% of weight of active material, at a temperature of the order of 20 to 80 ° C. . This polymerization operation has rapid kinetics; it generally lasts on the order of 1 to minutes. The aqueous solution obtained is then dried at a temperature of the order of 4,160 ° C, for a period such that the copolymer obtained has a loss at f measured at 700 ° C, of the order of 15 to 30%, of preferably of the order of 18 to 28% by mass. This drying operation can be carried out by any means, for example rotary oven, by atomization, in an oven, in a rapid mixer, in a "flash" dryer, in a fluidized ...

If necessary, the solid obtained can then be ground according to known techniques until a powder of particle size suitable for the detergent formulation is obtained which it will be incorporated. The average particle diameter can generally be around 150 to 600 μm. Said silicon polymer based on organomineral silicate copolymer, constituting the alkaline agent of the invention, can also be obtained by polymerization of a monomer composition consisting of at least one alkali metal silicate (A) and at least one alkoxysilane of formula (II); this polymerization operation can be carried out by drying a mixture of an aqueous solution of the metal silicate alca (A) containing of the order of 30 to 55%, preferably of the order of 35 to 50% of s weight of active ingredient and at least one alkoxysilane of formula (II); this drying operation is carried out at a temperature at least equal to that of the boiling point of the alcohol formed; a temperature of the order of 40 to 160 ° C is generally suitable; this operation is carried out for a period such that the copolymer obtained has a loss on ignition, measured at 700 ° C., of the order of 15 to 30%, preferably of the order of 18 to 28% of its mass. This drying operation can be carried out by any means, for example in a rotary oven, by atomization, in an oven, in a rapid mixer, in a "flash" dryer, in a fluidized bed ...

This polymerization operation can be accelerated by modifying the pH of the medium, by adding an acid, while being careful to maintain the solubility of the organomineral silicate copolymer in the medium.

If necessary, the solid obtained can then be ground until a powder, quickly and mainly soluble in water, of particle size adapted to the detergent formulation to which it will be incorporated. The average particle diameter can generally be of the order of 150 to 600 μm.

The present invention also relates to the use of the alkaline agent containing at least one silicon polymer based on the organomineral silicate copolymer described above, in detergent compositions, in particular for washing glass and dishes in the dishwasher. dishes. Said silicon polymer based on an organomineral silicate copolymer can be used in an amount of the order of 5 to 40%, preferably of the order of 10 to 40% by weight of said detergent compositions. Alkali metal silicates can be used in place of the alkaline agent and complexing agent in detergent formulations for washing in a dishwasher. Another subject of the present invention is the detergent compositions for protecting glass and tableware, characterized in that they contain at least one silicon polymer based on an organomineral silicate copolymer capable of being obtained by condensation polymerization.

- At least one ammonium or alkali metal silicate (A) with a Siθ2 M2θ molar ratio of the order of 0.5 to 4, preferably of the order of 1, 2 to 3.5, very particularly from 1, 2 to 3.3, the symbol M representing an ammonium cation or preferably an alkali metal

- And at least one organic silicon compound (B) chosen from

* the alkaline siliconates of formula (I) R _n Si (OM) _p (OH) ₄ . _n . _p (I) formula in which,

. R represents a similar or different hydrocarbon group containing from 1 to 20 carbon atoms, preferably from 1 to 18 carbon atoms, optionally halogenated and optionally containing one or more nitrogen or oxygen heteroatoms. M represents an ammonium cation or preferably an alkali metal

. (n + β) is less than or equal to 4, with n possibly ranging from 1 to 3 and β greater than or equal to 1,

* the condensates of the siliconates of formula (I), soluble in said ammonium or alkali metal silicate (A) in aqueous solution * the alkoxysilanes of formula (II)

R _n If (OR ') ₄ . _n (H) formula in which

. R and n have the same definition as above. R 'represents a linear or branched alkyl group containing from 1 to 6 carbon atoms, preferably methyl or ethyl, the respective amounts of ammonium silicate or of alkali metal (A) and of organic silicon compound (B) corresponding to a mass ratio of Si from the organic component / mass of total Si in the silicon polymer of the order of 0.0002 to minus 0.05, preferably of the order of 0.002 to 0.02, and very particularly of the order 0.003 to 0.006, said silicon polymer having a loss on ignition measured at 700 ° C. of the order of 15 to 30% by weight, preferably of the order of 18 to 28% by weight.

Examples of constituents (A) and (B) from which said silicon polymer based on organomineral silicate copolymer can be derived, as well as the method of preparation of the silicon polymer have already been mentioned above.

The detergent compositions forming the subject of the invention may contain around 5 to 40%, preferably around 10 to 40% of their weight of said silicon polymer (s) expressed as dry matter. In addition to the said silicon polymer (s) based on organomineral silicate copolymers, there may be present, in the said detergent compositions, the usual additives used in the composition of the detergent formulations for washing in the dishwasher. Mention may in particular be made of - surfactants in an amount which can range from 0.5 to 10%, preferably of the order of 1 to 5%, by weight of said composition expressed as dry matter; by these we can cite:

. anionic surfactants such as alkali metal soaps (alkalies of fatty acids in Ce - C24), alkali sulfonates (alkylbenzè sulfonates in Ce - C13, alkylsulfonates in C12 - Ciβ), fatty alcohols in C

C16 oxyethylenated and sulphated, C6 alkylphenols - C13 oxyethylenated and sulphated, alkali sulphosuccinates (C12 - C16 alkyl sulphosuccinates) .... non-ionic surfactants of the polyoxyethylenated C6 - C alkylphenols type, oxyethylenated aliphatic Ce - C22 alcohols, l ethylene oxide - propylene oxide block copolymers, optionally polyoxyethylenated amid carboxyls,. amphoteric surfactants of the alkyldimethyl - betaines type - "builders" (agents improving the surface properties of surfactants) of the type:

. organic phosphonates of the type of those of the DEQUEST® range of MONSANTO at a rate of at least 15% of the total weight of formulation expressed as dry matter,

. phosphates at a rate of at least 25% of the total weight of formulation expressed as dry matter,

. nitriloacetic acid up to approximately 10% of the total weight of formulation expressed as dry matter,. citric acid, gluconic acid or tartaric acid or their salts up to approximately 50% of the total weight of formulation expressed as dry matter,

- bleaching agents of the perborate type, percarbonates associated or not with N, N, N ', N'-tetraacetylethylenediamine (TAED) or chlorine products of the chloroisocyanura.es type up to approximately 30% of the total weight of said composition detergent expressed as dry matter,

anti-encrustation, anti-fogging or anti-stain agents of the acrylic acid and maleic anhydride copolymer type or acrylic acid homopolymers in an amount which can range up to approximately 10% of the total weight of said detergent composition expressed as dry matter, - fillers of the sodium sulfate type for powdered detergents in an amount which can range up to 50% of the total weight of said composition expressed as dry matter.

The present invention further relates to a method for cleaning glass and dishes in a dishwasher, using a detergent composition comprising from about 5 to 40%, preferably from about 10 to 40%. of its weight of said alkaline agent containing at least one silicon polymer based on an organomineral silicate copolymer described above.

The various additives which may be present alongside said alkaline agent have already been mentioned above.

The following examples are given by way of illustration.

Description of the glass corrosion test

This simplified glass corrosion test reproduces certain washing machine washing conditions, in particular the soaking, rinsing and drying cycles.

The glass used is made up of microscopy slides measuring 2.5 × 7.5 cm. This glass has the following chemical composition by weight: If: 21-43%

Ca: 2.8-5.8%

Mg: 1.6-3.4%

Na: 6.8-14.2% Al: 0.3-0.7%

The slide is half immersed and slightly tilted in 80 ml of aqueous washing solution, at room temperature, containing 5 g / l, expressed as dry, dissolved product, the more or less corrosive effect of which is to be tested.

If the product is initially solid, the slide is not introduced into the solution when the product is completely dissolved.

The container containing the half-submerged blade is then closed, then placed in an oven at 60 ° C for 3 weeks. Three times a week, the slide is taken out of the container, rinsed thoroughly with deionized water, then wiped with paper plunged back into the solution, the volume of which has been adjusted in the event that evaporation is produced.

At the end of the three weeks, the slide is weighed after cooling to room temperature and the variation in mass is calculated. The blade is observed and the following forms of corrosion are noted or not: iridescence, haze, streaks or frosted.

Finally, the pH of the solutions is measured at room temperature before immersing the slide and at the end of the experiment.

Comparative example 1

Three aqueous solutions are prepared at 5 g / l as dry product, of the following sodium disilicates: - product 1. disilicate in aqueous solution of SiO ₂ / Na ₂ O ratio = 2.1 contents

55% water by weight

- product 2. disilicate atomized to 20% water by weight

- product 3. disilicate dried in an oven at 80 ° C in a thin layer of 5 mm, containing 27% water by weight. The glass corrosion test described above is carried out, the results are as follows:

Product initial pH final pH Δ mass Observations

1 1 1, 6 1 1, 3 -2,1 mg opaque veil

2 11, 5 11, 3 -1, 6 mq opaque veil, iridescence

3 11, 6 1 1, 3 -1, 8 mq light veil, iridescence

It is found that the glass has undergone corrosion clearly visible to the naked eye, as well as a loss in mass. Comparative Example 2

Mixing: - 95 parts by weight expressed on a dry basis of a sodium silicate solution at

44.7% dry extract, Siθ2 / Na2θ ratio of 2

- and 5 parts by weight expressed on a dry basis of a potassium methylsiliconate solution at 45.1% of dry extract, marketed by RHONE-POULENC under the name

RHODORSIL 51T® Copolymerization takes place spontaneously.

After homogenization of the solution, partial evaporation of the water from the reaction mixture is carried out by drying in an oven at 105 ° C. for 48 hours. The loss on ignition at 700 ° C of the product is 18.3%.

The solid obtained called product 4. is ground into particles with an average diameter of around 200 μm.

An aqueous solution containing 5 g / l of said particles is subjected to the glass corrosion test described above.

The results are as follows:

Product initial pH final pH Δ mass Observations

4 11, 6 11.4 -3.8 mg haze

Example 3

We blend :

- 99 parts by weight expressed as dry matter of a sodium silicate solution containing 44.7% of dry extract, of Siθ2 Na2θ ratio of 2

- and 1 part by weight expressed on a dry basis of a potassium methylsiliconate solution containing 45.1% of dry extract, marketed by RHONE-POULENC under the name RHODORSIL 51T®

The copolymerization takes place spontaneously. After homogenization of the solution, partial evaporation of the water from the reaction mixture is carried out by drying in an oven at 105 ° C. for 48 hours. The loss on ignition at 700 ° C of the product is 24.5%.

The solid obtained, called product 5, is ground into particles with an average diameter of around 200 μm. An aqueous solution containing 5 g / l of said particles is subjected to the glass corrosion test described above. The results are as follows:

Product initial pH final pH Δ mass Observations

5 11, 4 11, 1 O mq no visible corrosion

It is found that the product 4 of Example 2 containing a relatively high amount of silicon of organic origin does not substantially protect the glass from corrosion while the product 5 of Example 3 containing only a small amount of silicon of organic origin completely protects the glass from corrosion.

Claims

1) Alkaline protective agent for glass and tableware, characterized in that it consists of at least one silicon polymer based on an organomineral silicate copolymer capable of being obtained by condensation polymerization - At least one ammonium or alkali metal silicate (A) with a Siθ2 M2θ molar ratio of the order of 0.5 to 4, preferably of the order of 1.2 to 3.5, the symbol M representing a cation ammonium or preferably an alkali metal - And at least one organic silicon compound (B) chosen from * the alkaline siliconates of formula (I) R _n Si (OM) _p (OH) ₄ . _n . _p (I) formula in which, . R represents a similar or different hydrocarbon group containing from 1 to 20 carbon atoms, preferably from 1 to 18 carbon atoms, optionally halogenated and optionally containing one or more nitrogen or oxygen heteroatoms. M represents an ammonium cation or preferably an alkali metal. (n + β) is less than or equal to 4, with n possibly ranging from 1 to 3 and β greater than or equal to 1, * the condensates of the siliconates of formula (I), soluble in said ammonium or alkali metal silicate (A) in aqueous solution * the alkoxysilanes of formula (II) R _n If (OR ') ₄ . _n (II) formula in which . R and n have the same definition as above. R 'represents a linear or branched alkyl group containing from 1 to 6 carbon atoms, preferably methyl or ethyl, the respective amounts of ammonium silicate or of alkali metal (A) and of organic silicon compound (B) corresponding to a mass ratio of Si originating from the organic compound / mass of total Si in the silicon polymer of the order of 0.0002 to less than 0.05, preferably of the order of 0.002 to 0.02, and very particularly of the order of 0.003 to 0.006, said silicon polymer having a loss on ignition measured at 700 ° C. of the order of 15 to 30% by weight, preferably of the order of 18 to 28% by weight. 2) An alkaline agent according to claim 1), characterized in that said alkali metal silicate (A) is a sodium silicate. 3) An alkaline agent according to claim 1) or 2), characterized in that said organic silicon compound (B) is chosen from . sodium or potassium methylsiliconates of formula CH3 Si (ONa) 3 CH3 Si (OIO3, sodium or potassium propylsiliconates of form C3H7 Si (ONa) 3 or C3H7 Si (OIO3, sodium or potassium butylsiliconates formula C4H9 If (ONa) 3 or C4H9 If (OK) 3, sodium or potassium hexylsiliconates of formula CβHi3 Si (ONa) 3 or CgH-13 If (OK) 3, sodium or potassium octylsiliconates of formula C8H17 Si (ONa) 3 or C8H17 Si (OK) 3, l sodium or potassium dimethylsiliconates of formula (CH3) 2 Si (ONa) 2 (CH3) 2 Si (OK) 2, sodium or potassium methylpropylsiliconates of form (CH3XC3H7) Si (ONa) 2 or (CH3XC3H7) If (OK) 2, sodium or potassium methylbutylsiiiconates of formula (CH3XC4H9) Si (ONa) 2 or (CH3) (C4Hg) Si (OK) 2, l methylhexylsiliconates of sodium or potassium of formula (CH3XC5H13) If (ON or (CH3) (C6H-j3) If (OK) 2, sodium or potassium methyloctylsiliconates formula (CH3) (C ₈ H ₁ ) Si (ONa) ₂ or (CH ₃ ) (C ₈ Hι ₇ ) If (OK) ₂ their mela nges and their condensates; . methyltrimethoxysilane of the formula CH 3 Si (OMe) 3, methyltriethoxysilane formula CH3 Si (OEt) 3, Toctyltriméthoxysilane formula C8H17 Si (OMe Toctyltriéthoxysilane formula C8H17 Si (OED3, diéthylènediaminetriéthoxysilane the formula H ₂ N- (CH 2) 2 H (CH ₂ ) 2-Si (OEt) _3. dimethyldimethoxysilane of formula (CH3) 2 Si (OMe) 2, trimethylmethoxysilane formula (^ 3) 3 Si (OMe), dimethyldiethoxysilane of formula (^ 3) 2 Si ( OEt) 2,, trimethylethoxysilane of formula (CH3) 3 Si (OEt). 4) Use as an alkaline protective agent of glass and dishes in detergent compositions, in particular for washing in the dishwasher, of a silicon polymer based on an organomineral silicate copolymer capable of being obtained by condensation polymerization - At least one ammonium or alkali metal silicate (A) with a molar ratio Siθ2 / M2θ of the order of 0.5 to 4, preferably of the order of 1.2 to 3.5, symbol M representing a cation ammonium or preferably an alkali metal - and at least one organic silicon compound (B) chosen from * alkaline siliconates of formula (I) R _n Si (OM) _p (OH) ₄ . _n . _p (I) formula in which, . R represents a hydrocarbon group, similar or different, containing from 1 to carbon atoms, preferably from 1 to 18 carbon atoms, optionally halogen and optionally containing one or more nitrogen or oxygen heteroatoms. M represents an ammonium cation or preferably an alkali metal. (û + β) is less than or equal to 4, with β possibly ranging from 1 to 3 and β greater than or equal to * the condensates of the siliconates of formula (I), soluble in said ammonium or alkali metal silicate (A) in aqueous solution * the alkoxysilanes of formula (II) R _n If (OR ') ₄ . _n (N) formula in which . R and n have the same definition as above . R 'represents a linear or branched alkyl group containing from 1 to 6 carbon atoms, preferably methyl or ethyl, the respective amounts of ammonium silicate or of alkali metal (A) and of organic silicon compound (B) corresponding to a mass ratio of Si from the organic compound / mass of total Si in the silicon polymer of the order of 0.0002 to less than 0.05, preferably of the order of 0.002 to 0.02, and more particularly of the order of 0.003 to 0.006, said silicon polymer having a loss on ignition measured at 700 ° C. of the order of 15 to 30% by weight, preferably of the order of 18 to 28% by weight. 5) Use according to claim 4), characterized in that said alkali metal silicate (A) is a sodium silicate. 6) Use according to claim 1) or 2), characterized in that said organic silicon compound (B) is chosen from . sodium or potassium methylsiliconates of formula CH3 Si (ONa) 3 or CH3 Si (OK) 3, sodium or potassium propylsiliconates of formula C3H7 Si (ONa) 3 or C3H7 Si (OK) 3, sodium butylsiiiconates or potassium of formula C4H9 Si (ONa) 3 or C4H9 Si (OK) 3, sodium or potassium hexylsiliconates of formula CβH ^ Si (ONa) 3 or C6H13 Si (OIO3, sodium or potassium octylsiliconates of formula C8H17 Si (ONa) 3 or C8H17 Si (OK) 3, sodium or potassium dimethylsiliconates of formula (CH3) 2 Si (ONa) 2 or (CH3) 2 Si (OK) 2, sodium or potassium methylpropylsiliconates of formula (CH3XC3H7) If (ONa) 2 or (CH3XC3H7) If (OK) 2, sodium or potassium methylbutylsiliconates of formula (CH3XC4H9) Si (ONa> 2 or (CH3XC4H9) If (OK) 2, methylhexylsiliconates of sodium or potassium of formula (CH3XC6H13) If (ONa) 2 or (CH3XC6H13) If (OK) 2, sodium or potassium methyloctylsiliconates of formula (CH ₃ ) (C ₈ H ₁₇ ) Si (ONa) or (CH3 ) (C ₈ H ₁₇ ) If (OK) ₂ their mixtures and their condensates; . methyltrimethoxysilane of formula CH3 Si (OMe) 3, methyltriethoxysilane of formula CH3 Si (OEt ^, Toctyltrimethoxysilane of formula C8H17 Si (OMe ^, Toctyltriethoxysilane of formula C8H-J7 Si (OE 3, diethylenediaminetriethoxysilane of formula H N- (CH2) 2-NH- (CH ₂ ) 2-Si (OEO3 . dimethyldimethoxysilane of formula (CH3) 2 Si (OMe) 2, trimethylmethoxysilanβ of formula (CH3) 3 Si (OMe), dimethyldiethoxysilane of formula (^ 3) 2 Si (OEt) 2. , trimethylethoxysilane of formula (CH3) 3 Si (OEt). of the silicone polymer constituting the alkaline agent forming the subject of any one of claims 1) to 3). 7) Use according to any one of claims 4) to 6), characterized in that said silicon polymer is used at a rate of the order of 5 to 40%, preferably of the order of 10 to 40% by weight of said compositions detergents. 8) Detergent protective composition for glass and tableware, characterized in that it comprises at least one silicon polymer based on an organomineral silicate copolymer capable of being obtained by condensation polymerization - at least one ammonium or alkali metal silicate (A) with a Siθ2 / M2θ molar ratio of the order of 0.5 to 4, preferably of the order of 1.2 to 3.5, the symbol M representing a ammonium cation or preferably an alkali metal - And at least one organic silicon compound (B) chosen from * the alkaline siliconates of formula (I) R _n Si (OM) _p (OH) ₄ . _n . _p (I) formula in which, . R represents a similar or different hydrocarbon group containing from 1 to 20 carbon atoms, preferably from 1 to 18 carbon atoms, optionally halogenated and optionally containing one or more nitrogen or oxygen heteroatoms. M represents an ammonium cation or preferably an alkali metal. (n + β) is less than or equal to 4, with β possibly ranging from 1 to 3 and β greater than or equal to 1, * the condensates of the siliconates of formula (I), soluble in said ammonium or alkali metal silicate (A) in aqueous solution * the alkoxysilanes of formula (II) R _n If (OR ') ₄ . _n (II) formula in which . R and β have the same definition as above. R 'represents a linear or branched alkyl group containing from 1 to 6 carbon atoms, preferably methyl or ethyl, the respective amounts of ammonium silicate or of alkali metal (A) and of organic silicon compound (B) corresponding to a mass Si ratio from the organic compound / total Si mass in the polymer of the order of 0.0002 to less than 0.05, preferably of the order of 0.002 to 0.02, and more particularly of the order of 0.003 to 0.006. said silicon polymer having a loss on ignition measured at 700 ° C. of the order of 15 to 30% by weight, preferably of the order of 18 to 28% by weight. 9) detergent composition according to claim 8), characterized in that said alkali metal silicate (A) is a sodium silicate. 10) Detergent composition according to claim 8) or 9), characterized in that said organic silicon compound (B) is chosen from . sodium or potassium methylsiliconates of formula CH3 Si (ONa) 3 or CH3 Si (OK) 3, sodium or potassium propylsiliconates of formula C3H7 Si (ONa) 3 or C3H7 Si (OK ^, sodium butylsiliconates or of potassium of formula C4H9 Si (ONa) 3 or C4Hg Si (OIO3, sodium or potassium hexylsiliconates of formula C _β Hi3 Si (ONa) 3 or CeH- _| 3 Si (OIO3, sodium or potassium octylsiliconates formula C8H17 Si (ONa) 3 or C8H17 Si (OK) 3, the sodium or potassium dimethylsiliconates of formula (CH3) 2 Si (ONa) 2 or (CH3) 2 Si (OK) 2, sodium or sodium methylpropylsiliconates potassium of formula (CH3XC3H7) If (ONa) 2 or (CH3XC3H7) If (OK) 2, sodium or potassium methylbutylsiliconates of formula (CH3XC4H9) Si (ONa) 2 or (CH3XC4H9) If (OK) 2, methylhexylsiliconates sodium or potassium formula (CH3XC6H13) If (ONa) 2 or (CH3XC6H13) If (OK) 2, sodium or potassium methyloctylsiliconates of formula (CH ₃ ) (C ₈ H ₁₇ ) Si (ONa) ₂ or (CH ₃ ) (C ₈ H _{1 7} ) If (OK) ₂ their mixtures and their condensates; . methyltrimethoxysilane of formula CH3 Si (OMe) 3, methyltriethoxysilane of formula CH3 Si (OE 3, Toctyltrimethoxysilane of formula C8H17 Si (OMe) 3, Toctyltriethoxysilane of formula C8H17 Si (OEt) 3, diethylenediaminetriethilysilethine N ) 2-NH- (CH) 2-Si (OEt) ₃ . dimethyldimethoxysilane of formula (^ 3) 2 Si (OMe) 2, trimethylmethoxysilane of formula (^ 3) 3 Si (OMe), dimethyldiethoxysilane of formula (CH3) 2 Si (OE 2,, trimethylethoxysilane of formula (^ 3 ) 3 If (OEt). 11) Detergent composition according to any one of claims 8) to 10), characterized in that it contains order of 5 to 40%, preferably order of 10 to 40% of its weight of said silicon polymer. 12) detergent composition according to any one of claims 8) to 11), characterized in that it also contains at least one additive chosen from the agents surfactants, "builders" (agents improving the surface properties of surfactants, bleaching agents, anti-encrustation agents, fillers. 13) Method for cleaning glass and dishes in a dishwasher, with a detergent composition comprising of the order of 5 to 40%, preferably the order of 10 to 40% of its weight of said alkaline agent making the object of any of claims 1) to 3).