EP0165136A1 - Detergent compositions containing copolymers based on polyoxyethylene and polyoxyalkylene used as antisoil redeposition agents, and process for their preparation - Google Patents

Abstract

The present invention relates to detergent compositions comprising at least one anti-depositing polymer. It relates more particularly to detergent compositions which contain at least one anti-depositing polymer useful in washing synthetic organic polymeric materials which comprises at least one unit chosen from the group: ethylene oxide, alkylene oxide and which gives the fiber a zeta potential value relative to the zeta potential of the bare fiber less than or equal to 0.5 for a minimum quantity of adsorbed polymer per gram of tissue of 0.02 mg.

Description

The present invention relates to copolymers based on polyoxyethylene and polyoxyalkylene used as anti-deposition agents in the washing of textiles.

These ccpolymers are used more particularly as an antiredepositing agent for washing aqueous, polymeric, organic and synthetic materials.

It is known that polymeric, synthetic organic materials are difficult to clean in an aqueous medium. In fact, during successive washes, the particles of dirt suspended in the detergent medium are permanently and almost irreparably deposited on these textiles, the consequence is that these textiles lose their whiteness and their luster over time in a very more marked than natural textiles such as cotton.

The present invention, which has overcome all of these technical problems, relates to detergent compositions characterized in that they contain at least one antiredepositing copolymer useful in particular for washing synthetic organic polymeric materials which comprises at least one unit chosen from the oxide group. ethylene, alkylene oxide and which reduces the zeta potential of the textile fiber to a value less than or equal to 0.5 times the zeta potential of the bare fiber; the compositions being used under conditions such that the amount of copolymer adsorbed per gram of tissue is at least 0.02 mg.

Throughout the rest of the text, the term zeta potential is understood to mean the absolute value of this parameter.

The copolymers which meet the definition of the invention fall into four main groups which do not limit the concept of the invention.

They all present preferentially. a molecular mass less than or equal to 150,000 and even more preferably between 2,000 and 150,000 and even more particularly between 4,000 and 100,000.

The copolymers according to the invention preferably contain an amount by weight of ethylene oxide relative to the polymer of between 10% and 90% and even more preferably an amount between 30 and 90% and very particularly an amount between 40 and 70%.

The ethylene oxide groups constitute the hydrophilic part of the copolymer and therefore allow the solubilization of the copolymer in water which is essential for a detergency application in an aqueous medium. The alkylene oxide groups constitute the hydrophobic part of the copolymers and allow the adsorption of the copolymer on the fiber made up of synthetic organic polymers. This adsorption of the copolymer on the fiber will allow the desired effect, that is to say the anti-deposition.

The first group of copolymers which can be used according to the invention consists of copolymers composed of linear or branched polyoxyethylene and polyoxyalkylene blocks containing in particular from 3 to 6 carbon atones per alkylene group. The alkylene groups are preferably propylene or butylene groups.

These copolymers sold under the trademark "PLURONICS" ® are prepared in a known manner, for example according to the process described in US Pat. No. 2,674,619. They are used for the most part and essentially for polyoxyethylene-polyoxyalkylene copolymers as a removal agent dirt, we had never used, as an anti-depositing agent, some of them which reduce the zeta potential of the fiber to a value less than or equal to 0.5 times the zeta potential of the bare fiber.

dans laquelle :

• - R₁ R_{2 R3} R₄ R₅ R₆ représentent des polymères choisis parmi les homnpolymères polyoxyéthylène, polyoxyalkylène linéaires ou ramifiés concenant de 3 à 6 atomes de carbone et les copolymères blocs linéaires ou ramifiés polyoxyéthylène polyoxyalkylène.
• - n, m et p sont des nombres entiers égaux ou supérieurs à 0 et égaux ou inférieurs à 10 et de préférence dont la somme n + m + p est comprise entre 1 et 20 et avantageusement entre 1 et 5.

The second group of copolymers which can be used according to the invention consists of copolymers which correspond to the general formula (I)

in which :

• - R ₁ R _{2 R3} R ₄ R ₅ R ₆ represent polymers chosen from polyoxyethylene, linear or branched polyoxyalkylene homnpolymers containing 3 to 6 carbon atoms and linear or branched polyoxyethylene polyoxyalkylene block copolymers.
• - n, m and p are whole numbers equal to or greater than 0 and equal to or less than 10 and preferably the sum of which n + m + p is between 1 and 20 and advantageously between 1 and 5.

It is more particularly preferred to use the compounds for which p = 0, m = 0 and n = 1.

The polyoxyalkylene groups are preferably chosen from polyoxypropylene and polyoxybutylene.

The copolymers of formula (I) can optionally be made ionizable by quaternizing the nitrogen atom (s). This quaternization can be carried out for example by a hydrogen atom or by an alkyl group.

Some of these copolymers are marketed under the name TETEONIC.

They are used in the same way as PLURONICS® as a soil removal agent, but they have never been used for their anti-depositing properties.

dans laquelle :

• - R₇, R₈ représentent un groupe méthyle ou des polymères choisis parmi les homopolymères polyoxyéthylène-polyoxyalkylène linéaires ou ramifiés contenant notamment de 3 à 6 atomes de carbone et les copolymères blocs linéaires ou ramifiés polyoxyéthylène_- polyoxyalkylène.
• - a est un nombre entier compris entre 1 et 150
• - au moins un atome de silicium porte un groupe choisi parmi R₇ et R₈.

The third group of copolymers which can be used according to the invention consists of copolymers which correspond to the general formula (II)

in which :

• - R ₇ , R ₈ represent a methyl group or polymers chosen from linear or branched polyoxyethylene-polyoxyalkylene homopolymers containing in particular from 3 to 6 carbon atoms and linear or branched polyoxyethylene _- polyoxyalkylene block copolymers.
• - a is an integer between 1 and 150
• at least one silicon atom carries a group chosen from R ₇ and R ₈ .

The copolymers of formula (II) sold are prepared in a manner known per se, for example described in US Patent No. 2,970,150, Example 16.

dans laquelle :

• - R₉, R₁₀ représentent des polymères choisis parmi les homo- polynères polyoxyéthylène - polyoxyalkylène linéaires ou ramifiés contenant notamment de 3 à 6 atomes de carbone et les copolymères blocs linéaires ou ramifiés polyoxyéthylène - polyoxyalkylène, chacun des groupes R₉ R₁₀ pouvant être différent d'un motif à l'autre.
• - A représente un radical alkylène ou phénylène éventuellement substitué.

The fourth group of copolymers which can be used according to the invention consists of block copolymers formed by a series of units corresponding to the general formula (III) _:

in which :

• - R ₉ , R ₁₀ represent polymers chosen from linear or branched polyoxyethylene - polyoxyalkylene homopynyners containing in particular from 3 to 6 carbon atoms and linear or branched polyoxyethylene - polyoxyalkylene block copolymers, each of the groups R ₉ R ₁₀ may be different from one motif to another.
• - A represents an optionally substituted alkylene or phenylene radical.

The polyoxyalkylenes can be chosen in particular from polycxypropylenes.

Among the copolymers of formula (III), mention may be made of those for which A represents a hexamethylene, toluylene, isophorne, diphenylalkane radical.

It is particularly preferred to use the copolymers of formula (III) in which A is a hexamethylene or toluylene radical.

According to the invention, it is preferred to use, among the group 4 copolymers, those which have: a molecular mass of between 4,000 and 40,000 and very particularly between 4,000 and 25,000, a weight amount of ethylene oxide of between 40 and 50%, polyoxyethylene blocks with molecular masses less than 3,500 and even more preferably between 550 and 1,600 and polyoxyalkylene blocks with molecular masses less than 4,000 and preferably between 500 and 2,000.

The copolymers of formula (III) are obtained for example by condensation of polyoxyethylene and polyoxyalkylene or of polyoxyethylene - polyoxyalkylene copolymers as defined in the first group of copolymers according to the invention with diisocyanates chosen from hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, di (isocyanatophenyl) alkanes, in an anhydrous medium in the presence of tin salt.

The copolymers obtained by condensation of the homopolymers with diisocyanates have markedly improved anti-depositing properties.

The copolymers described above can be used according to the invention as anti-depositing agents when they lower the zeta potential of the textile fiber to a value less than or equal to 0.5 times the zeta potential of the bare fiber. This decrease in zeta potential is a function of the amount of copolymer adsorbed. This amount must be greater than 0.02 mg / g.

The quantity adsorbed is measured by bringing a sample of fabric made of polymeric, organic, synthetic material (TERGAL® type) of a mass close to 3.5 g fixed on a metallic support, with 100 ml of a NaCl solution. (3 g / 1) containing the polymer, in a cell thermostatically controlled at 25 ° C. The environment is agitated. When the adsorption equilibrium is reached, the quantity adsorbed is determined by an assay of the concentration of polymer remaining in solution according to the method described by BALEUX (C.R. Acad. Sc., 274 series C, (1972), 1617).

The zeta potential of the fiber is measured before contact with the copolymer and after contact.

The measurements of zeta potential, or electrokinetic potential are carried out by the method of flow potential: a NaCl solution 3 g / l (pH = 7) containing or not the polymer circulates under the effect of a pressure through a buffer consisting of several superimposed fabric washers. The variation of the potential difference at the ends of the buffer as a function of the pressure applied to the solution makes it possible to determine the zeta potential of the fibers (J.S. STANLEY J. Phys. Chem. 58, (1954), 533).

Before measuring the electrokinetic potential, the tissue washers are brought into contact for 24 hours with a polymer solution in NaCl medium 3 g / 1, so as to adsorb the copolymer on the fibers. After this adsorption phase, the washers of tissue are placed in the filter of the apparatus and the copolymer solution used during the adsorption period circulates under the effect of a pressure through the tissue pad.

The operation is carried out in the same way with fabric washers not impregnated with copolymer.

The anti-depositing effect of the copolymer can be measured by a series of different tests in the presence of dirt.

It is not obvious, on reading the prior art, to relate the effectiveness of the copolymer and therefore its antiredepositing effect to the zeta potential of the fiber in polymeric, organic, synthetic material on which the copolymer is adsorbed.

It has been discovered by the present invention that the anti-depositing effect is achieved when the zeta potential of the fiber on which the copolymer is adsorbed is equal to or less than 0.5 times that of the bare fiber.

This reduction in zeta potential is achieved for amounts of adsorbed copolymer equal to or greater than 0.02 mg / g of tissue. The preferred amount of adsorbed copolymer varies with the type of adsorbed copolymer.

For the copolymers of the first group consisting of polyoxyethylene and polyalkylene copolymers, the preferred amount of adsorbed copolymer is between 0.1 and 5 mg / g of tissue.

For the copolymers of the second group corresponding to the general formula (I), the preferred amount of adsorbed copolymer is between 0.02 and 5 mg / g of tissue.

For the copolymers of the third group corresponding to the general formula (II), the preferential amount of adsorbed copolymer is greater than approximately 0.3 mg / g and even more preferably between 0.4 and 5 mg / g of tissue.

For the copolymers of the fourth group corresponding to the general formula (III), the preferred amount of adsorbed copolymer is between 0.05 and 5 mg / g of tissue.

The invention will now be described more fully without however limiting its scope, using the anti-deposition tests used and the examples which will follow.

anti-deposition weights used ballast n ° 1

5 ml of a carbon black suspension (black) are successively introduced into a cell thermostatically controlled at 25 ° C. containing 100 ml of a SaCl solution (3 g / 1) and a concentration of 50 mg / 1 of antireplacement agent. "PRINTEX U" ®, concentration 200 mg / 1) previously dispersed with ultrasound and a fabric sample (polyester of TERGAL type, m - 0.5 g) fixed on a metal support. The agitatior of the medium is ensured by a magnetic bar.

After 30 min of contact, the support carrying the tissue sample is removed and immersed in 100 ml of distilled water stirred by a magnetic bar. This rinsing operation lasts three ninutes.

The deposition on the textile fibers is evaluated by the difference ΔR (measured by a "ELREPHO" photometer from ZEISS®, filter No. 10) between the reflectance of the initially clean fabric and that of the fabric after contact with the suspension of carbon black.

The higher Δ R, the greater the deposition. In the absence of a copolymer, the value of Δ R is 40. It can be considered that an anti-depositing additive has good efficacy during this test if it reduces AR to a value between 10 and 18, below 10 , the performance of the additive is excellent.

ballast n ° 2

The anti-depositing efficacy of an additive is evaluated by carrying out five cumulative "Terg-O-Tometer" washing cycles (United States Testing Company Inc. Hobokin, NJ) in the presence of "complete" soiling,

Each cycle consists of a 20-minute washing phase (1 1 of solution per pot, T = 60 ° C) and a five-minute rinse in cold hard water. Soiling is introduced into each pot five minutes after the start of each cycle. The hardness of the water used is 32 ° excl.

• 100 g Sebum
• 4 g Acide oléique
• 8 g Triethanolamine
• 4 g Salissure particulaire
• 884 g Eau

The soiling used is of the "Spangler" type (WG SPANGLER, ED CROSS and BR SCHAAFSMA, J. Am. Oil Chemist's Soc. 42 (1965), - 723), it consists of:

• 100 g Sebum
• 4 g Oleic acid
• 8 g Triethanolamine
• 4 g Particulate soiling
• 884 g Water

• 10 % Acide palmitique
• 5 % Acide stéarique technique
• 10 % Acide oléique purifié
• 5 % Acide linoléique
• 15 % Huile de Coprah
• 20 % Huile d'olive vierge
• 5 % Squalène 90 %
• 10 % Paraffine raffinée 52/54
• 15 % Blanc de baleine
• 5 % Cholesterol

The composition of sebum is as follows:

• 10% Palmitic acid
• 5% Technical stearic acid
• 10% Purified oleic acid
• 5% Linoleic acid
• 15% Copra Oil
• 20% virgin olive oil
• 5% Squalene 90%
• 10% Refined paraffin 52/54
• 15% Whale white
• 5% Cholesterol

• 86 % Kaolin
• 8 % Noir de funée
• 4 % Oxyde de fer noir
• 2 % Oxyde de fer jaune.

The composition of the particulate soiling is as follows:

• 86% Kaolin
• 8% Funée black
• 4% Black iron oxide
• 2% Yellow iron oxide.

The total soil concentration used is 50 g / l for each washing cycle.

The concentration of detergent used is 6 g / l, its hanging composition is as follows:

The fabric samples used during our washing tests are polyester samples ("DACRON @ 54" from TESTFABRIC) washed beforehand at 60 ° C in a machine supplied with fresh water and in the absence of detergent. Each pot of the "Terg-0-Tometer" contains 6 rectangles of fabric (10 x 12 cm).

The concentration of anti-depositing additive used is 50 mg / 1. The redeposition is quantified by the difference A R (measured by a GARDNER photometer, filter Y) between the reflectance of the initially clean fabric and that of the fabric after five washing cycles. The anti-depositing agent is all the more effective when Δ R is low.

Test # 3

The experimental conditions used during this test are identical to those of the previous test, with the difference that the stain is no longer a liquid stain of the "Spangler" type but a stain impregnated on cotton samples ("WFK Testgewebe GmbH KREFELD "). Before each washing cycle, three rectangles (10 x 12 cm) of soiled cotton are placed in each pot.

For tests 2 and 3, it can be considered that an additive has a significant anti-depositing effect if the value of A R is reduced by at least 3 points in the presence of the polymer compared to the value of A R measured in the absence of additive.

The values of the ratio ξ / ξ _o (ξ is the zeta potential of the fiber in the presence of copolymer and ξ _o represents the zeta potential of the bare fiber) and of the amount adsorbed per gram of tissue, indicated in the examples below , were determined under conditions where the quantity adsorbed is close to its maximum value, which corresponds in the experimental conditions set work, at copolymer concentrations within the solution of the order of 10 mg / 1.

Examples 1 to 10 Group 1 products

Table 1 gives the results of the anti-depositing effect (AR) measured according to test 1 of products marketed under the brand PLURONICS®. The products for which ξ / ξ _o is less than 0.50 (examples 1, 2, 3, 5) have an anti-depositing effect markedly improved compared to those which do not meet the criteria of the invention. Example 6 shows in particular that Pluronic L 64 known to have a good soil removal effect does not meet the criteria of the invention.

Examples 11 to 18 Group 2 products

Examples 11 to 16 were carried out with products consisting of ethoxypropylated ethylene diamines, produced according to the general formula (I) in which n = 1, m = p = o and R ₁ = RZ ⁼ R ₄ = R ₆ ⁼ ( ^C ₃ ^H ₆ ⁰ ) _x (C ₂ H ₄ O) _y H. These products are sold under the name TETROHIC. Tests 11, 12, 15 and 16 are in accordance with the invention.

Example 17 was carried out using a product corresponding to the general formula (I) in which n = 1, m = p = O, R ₁ = R ₂ ⁼ R ₄ = R ₆ = (C ₃ H ₆ O) _x (C ₂ H ₄ O) _y H and marketed under the name LUTEKSOL®; it is in accordance with the invention.

Example 18 was carried out on an ethoxypropylated triethylenetetramine, product corresponding to the general formula (I) in which n = n = p = 1, R ₁ = R ₂ = R ₃ = R ₄ = R ₅ = R ₆ = ( C ₃ H ₆ O) _x (C ₂ H ₄ O) _y H; it conforms to the invention.

Tests 11 to 18 are reported in Table 2.

Here again, it can be seen that the products having a ratio ξ / inférieure _{o of} less than 0.5 have a very improved anti-depositing effect compared to those which do not meet the criteria of the invention.

Example 19 - Group 3 product

Example 19 was carried out using a product corresponding to the general formula (II) in which a = 12 and in which 4 homopolymers of ethylene oxide of molecular mass equal to 550 were fixed.

Test 19 is reported in Table 3.

This table shows that the value of ζ / ζ _o obtained in the presence of this product is 0.4 for an adsorbed amount of 0.44 mg of copolymer per gram of tissue, which leads to good anti-depositing efficacy (AR = 15 , 1). This product therefore meets the criteria of the invention.

Examples 20 to 59 Group 4 products

Examples 20 to 33 were carried out using copolymers obtained by condensation of products of group 1 PLURONICS® by means of hexanethylene diisocyanate (HDI) at a temperature between 80 and 105 ° C in the optional presence of a catalyst such as dibutyltin dilaurate. Tests 20 to 33 are reported in Table 4a.

These products have an anti-depositing effect and lead to values of ζ / ζ _o less than 0.5. They meet the criteria of the invention.

Examples 34 to 58 were carried out using copolymers obtained by condensation of polyoxyethylene and polyoxyalkylene in the presence of hexanethylene diisocyanate. Tests 34 to 58 are reported in Table 4b, 4c and 4d.

It is noted that particularly good results are obtained for the copolymers having a quantity by weight of ethylene oxide of between 40 and 50% and a molecular mass comprised between 4000 and 25000. This is the case of tests 38, 39, 40 , 54 and 55.

The invention also relates to the preparation of detergent compositions comprising the copolymers of the type described above, a simple and effective preparation process has been developed.

The process for preparing detergent compositions of the type of the invention is characterized in that the anti-depositing copolymer is added to a slurry comprising other constituents of the compositions, the mixture thus obtained is then dried.

It has been observed that the copolymer thus introduced retains all of these properties in the composition obtained. This is an advantageous advantage because the copolymers of the invention can be used without appreciably modifying the conventional methods of preparation of detergent compositions.

The preparation of the slurry is done in a manner known per se. The copolymer is added thereto with stirring. The mixture obtained is then dried by any suitable means.

To the dry product thus obtained, it is possible to mix any usual additive used in detergent compositions: bleaching agents, anti _- foaming agent, perfumes, dyes, enzymes for example.

The amount of copolymer added is such that it represents 0.2 to 5% approximately and preferably between 1 and 2% by weight of the final composition.

When added to the slurry, the copolymer can be presented in different forms.

A first possibility consists in presenting the copolymer in the form of a solution in water. In such a case, the concentration of copolymer in the solution is between 5 and 20% and preferably 10 to 15%.

Another possibility is to prepare a solution of the copolymer in a water-alcohol mixture.

As alcohol, an aliphatic alcohol can be used such as for example ethanol or a compound which can be used in detergency as a nonionic surfactant such as for example polyoxyethylenated alkylphenols, polyoxyethylenated aliphatic alcohols, glycols and polyglycols.

Generally a mixture of 40-60% copolymer, 20-50% water, 5-15% alcohol, preferably 50% copolymer, 40% water, 10% alcohol, is used.

It is also possible to present the copolymer on a support. In this case, it is possible to use as support a suitable silica, for example a silica of the TIXOSIL 38A type.

It is also possible to use mixtures of the copolymer and of sulfonic acids such as, for example, arylsulfonic, alkylsulfonic or alkylarylsulfonic acids, in particular linear alkylbenzene sulfonic acids.

An example of preparation of a composition according to the invention will now be given.

The various constituents of the composition are given below with the percentages by weight.

First of all, a slurry is prepared comprising LABS and sodium sulphate, stearate, silicate and tripolyphosphate by stirring for 20 minutes at 85 -90 ° C.

We then operate in 3 cases.

CASE 1

In the first case, the antiredepositing agent according to the invention is not added to the formulation. The slurry is then dried at 4 hours at 150 ° C. and then mixed with the other constituents of the composition.

CASE 2

In this case, an antiredeposition agent is added with stirring for 15 minutes at 80 ° C. in the form of a 10 × solution in water according to the invention. This agent is that corresponding to Example 39 (copolymer obtained by condensation of polyoxyethylene and polyoxyalkylene in the presence of hexamethylene diisocyanate).

The slurry thus prepared is mixed after drying (4 hours at 150 ° C) with the other components of the composition.

CASE 3

In this case, no more anti-depositing agent is added and the procedure is as in the first case. However, the same agent is added as in case 2 to the washing medium before each washing cycle.

Washings and reflectance measurements are then carried out according to the conditions of test 3 of the main patent.

In cases 2 and 3, the amount of antirepleting agent used represents 1 X of the total weight of the composition. The concentration of the washing composition is 6 g / l.

The reflectance Ry of the textile is evaluated after washing. The higher the reflectance Ry, the lower the redeposition. The results are given below:

It can therefore be seen by comparing cases 2 and 3 that the anti-redeposition agent according to the invention can therefore completely be incorporated into a slurry without any significant impact on its properties.

Of course, it is understood that the preparation process which has just been described is only a particular and advantageous process, it is quite possible to envisage other processes for preparing the compositions described above without going out of the scope of the invention.

Furthermore, the invention is in no way limited to the embodiments described which have been given only by way of examples. In particular, it includes all the means constituting equi- technical alents of the means described as well as their combinations if these are used in the context of protection as claimed.

Claims (31)

1. Detergent compositions characterized in that they contain at least one antiredepositing copolymer useful in particular for washing synthetic organic polymeric materials, which comprises at least one unit chosen from the group ethylene oxide, alkylene oxide and which reduces the zeta potential of the textile fiber to a value less than or equal to 0.5 times the zeta potential of the bare fiber, the compositions being used under conditions such that the amount of copolymer adsorbed per gram of fabric is at least 0, 02 mg. 2. Compositions according to claim 1, characterized in that the (s) copolymer (s) has a molecular mass less than or equal to 150,000. 3. Compositions according to claim 2, characterized in that the (s) copolymer (s) has a molecular weight of between 2,000 and 150,000. 4. Compositions according to claim 3, characterized in that the copolymer (s) has a molecular weight of between 4,000 and 100,000. 5. Compositions according to any one of the preceding claims, characterized in that the copolymer (s) comprises a quantity by weight of ethylene oxide of between 10 and 90%. 6. Compositions according to claim 5, characterized in that the (s) copolymer (s) comprises a weight amount of ethylene oxide of between 30 and 90%. 7. Compositions according to claim 6, characterized in that the (s) copolymer (s) comprises a weight amount of ethylene oxide of between 40 and 70%. 8. Compositions according to any one of the preceding claims, characterized in that the copolymer (s) is composed of linear or branched polyoxyethylene and polyoxyalkylene blocks containing from 3 to 6 carbon atoms. 9. Compositions according to claim 8, characterized in that the (s) copolymer (s) is composed of polyoxyethylene and polyoxypropylene blocks. 10. Compositions according to any one of claims 1 to 7, characterized in that the co-copolymer (s) corresponds to the general formula (I).

in which : - R ₁ R ₂ R ₃ R ₄ R ₅ R ₆ represent polymers chosen from polyoxyethylene, linear or branched polyoxyalkylene homopolymers containing from 3 to 6 carbon atoms and polyoxyethylene - polyoxyalkylene linear or branched block copolymers - nmp are whole numbers equal to or greater than 0 and equal or less than 10 and the sum n ÷ m + p of which is preferably between 1 and 20. 11. Compositions according to claim 10 characterized in that in the general formula (I) the sum n + m + p is between 1 and 5. 12. Compositions according to claims 10 and 11 characterized in that in the general formula (I) n = 1, m = p = 0. 13. Compositions according to any one of claims 10 to 12 characterized in that the copolymer is composed of polycxyethylene - polyoxypropylene or polyoxybutylene blocks. 14. Compositions according to one of claims 10 to 13 characterized in that in formula (I) the nitrogen atoms are cuaternized. 15. Compositions according to any one of claims 1 to 7, characterized in that the copolymer (s) corresponds to the general formula (II)

in which : - R ₇ R ₈ represent polymers chosen from linear or branched polyoxyethylene, polyoxyalkylene homopolymers con containing 3 to 6 carbon atoms and the linear or branched polyoxyethylene - polyoxyalkylene block polymers. - a is an integer between 1 and 150. - at least one silicon atom carries a group chosen from R and ^R 8. 16. Compositions according to any one of claims 1 to 7, characterized in that the copolymers comprise at least one unit corresponding to the general formula (III)

in which - R ₉ R ₁₀ represent polymers chosen from polyoxyethylene, linear or branched polyalkylene homopolymers containing 3 to 6 carbon atoms and linear or branched polyoxyethylene - polyoxyalkylene block copolymers - A represents an optionally substituted alkylene or phenylene radical. 17. Compositions according to claim 17 characterized in that the polyoxyalkylenes are polyoxypropylenes. 18. Compositions according to claims 16 to 17 characterized in that the copolymers have a molecular weight of between 4,000 and 25,000. 19. Compositions according to claim 16 to 18, characterized in that the copolymers comprise a quantity by weight of ethylene oxide of between 40 and 50%. 20. Compositions according to Claims 16 to 19, characterized in that the copolymers contain polyoxyethylene blocks with a molecular mass of less than 3,500 and preferably between 550 and 1,600. 21. Compositions according to claim 16 to 19, characterized in that the copolymers contain polyoxyalkylene blocks with a molecular mass of less than 4,000 and preferably between 500 and 2,000. 22. Compositions according to any one of claims 8 to 9 characterized in that they reduce the potential of the fiber to. a value less than 0.5 times the zeta potential of the bare fiber when used under conditions such that the amount of copolymer adsorbed per gram of tissue is between 0.1 mg and 5 mg / g. 23. Compositions according to any one of claims 10 to 14, characterized in that they reduce the zeta potential of the fiber less than 0.5 times the zeta potential of the bare fiber by being used under conditions such as the amount of copolymer adsorbed per gram of tissue is between 0.02 and 5 mg / g. 24. Compositions according to claim 15, characterized in that they reduce the zeta potential of the fiber to a value less than 0.5 times that of the zeta potential of the bare fiber by being used under conditions such as the amount of copolymer adsorbed per gram of tissue is greater than about 0.3 ng and preferably between 0.4 and 5 mg / g. 25. Compositions according to any one of claims 16 to 21 characterized in that they reduce the zeta potential of the fiber to a value less than 0.5 times that of the zeta potential of the bare fiber by being used under such conditions that the amount of copolymer adsorbed is between 0.05 and 5 mg / g. 26. A method of preparing detergent compositions according to any one of the preceding claims, characterized in that the antiredepositing copolymer is added to a slurry comprising other constituents of the composition and in that the mixture obtained is then dried. 27. The method of claim 26 characterized in that the copolymer is added to the slurry in the form of a solution in water. 28. The method of claim 26 characterized in that the copolymer is added to the slurry in the form of a solution in a water-alcohol mixture. 29. A method according to claim 28 characterized in that a compound which can be used as a nonionic surfactant is used as alcohol. 30. The method of claim 26 characterized in that the added copolymer is presented on a silica support. 31. The method of claim 26 characterized in that the added copolymer is presented in the form of a mixture with a compound chosen from the group of sulfonic acids.