FR2564852A1 - Detergent compositions comprising ethylene oxide/alkylene oxide polymers as antiredepositing agents - Google Patents

Abstract

The present invention relates to detergent compositions comprising at least one antiredepositing polymer. It more particularly relates to detergent compositions which contain at least one antiredepositing polymer, which is useful in washing synthetic organic polymeric substances, which contains at least one unit chosen from the group: ethylene oxide or alkylene oxide and which gives a zeta potential value to the fibre which, with respect to the zeta potential of the bare fibre, is less than or equal to 0.5 for a minimum quantity of adsorbed polymer per gram of fabric of 0.02 mg.

Description

POLY! ERES ETHYLENE OXIDE - ALKYLENE OXIDE
AS ANTIREDEPENDENT AGENT
The present invention relates to polymers based on ethylene oxide - alkylene oxide used as anti-redepositing agent in the washing of textiles.

 These polymers are used more particularly as antiredepositant agent for washing in aqueous medium polymeric, organic, synthetic materials.

 It is known that polymeric, synthetic organic materials are difficult to clean in an aqueous medium. Indeed, during successive washings, the soil particles suspended in the washing medium are deposited permanently and almost irreparably on these textiles, the consequence is that these textiles lose their whiteness and brightness over time so much more marked than natural textiles such as cotton.

 The present invention which has overcome all these technical problems relates to detergent compositions characterized in that they contain at least one anti-redepositing polymer useful in particular for washing synthetic polymeric organic materials which comprises at least one unit selected from the group oxide of ethylene, alkylene oxide and which gives the textile fiber a zeta potential value with respect to the zeta potential of the bare fiber less than or equal to 0.5 for a minimal amount of polymer adsorbed per gram of tissue of 0.02 mg .

 The polymers that meet the definition of the invention can be grouped into four main groups that are not limiting of the concept of the invention.

 They all preferably have a molecular weight 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 polymers according to the invention preferably comprise an amount by weight of ethylene oxide relative to the polymer of between 10% and 90% and even more preferably of between 30 and 90%, and especially of between 40 and 70%.

 The ethylene oxide groups constitute the hydrophilic part of the polymer and thus allow the solubilization of the polymer in water which is essential for a detergent application in an aqueous medium. The alkylene oxide groups constitute the hydrophobic part of the polymers and allow the adsorption of the polymer on the fiber composed of synthetic organic polymers. This adsorption of the polymer on the fiber will allow the desired effect, that is to say antiredeposition.

 The first group of polymers that may be used according to the invention are copolymers composed of linear or branched alkylene oxide-alkylene oxide blocks containing in particular from 3 to 6 carbon atoms per alkylene group. The alkylene groups are most preferably propylene or butylene groups.

 These polymers marketed under the trade name "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 polymers ethylene oxide - alkylene oxide. as a soil-removing agent, some of them which have responded to a zeta potential value of less than 0.5 have never been used as anti-redeposition agents.

dans lacuelle
- R1 R2 R3 R4 R5 R6 identiques ou différents représentent des polymères choisis parmi les homopolymères oxyde d'éthylène, oxyde d'alkylène linéaire ou ramifié contenant de 3 à 6 atomes de carbone et les copolymères blocs linéaires ou ramifiés oxyde d'éthylène oxyde d'alkylène
- n, m et p sont des nombres entiers égaux ou supérieurs à O et égaux ou inférieurs à 10 (O < n xC 10) et de préférence dont la somme n + m . p est inférieure à 20 et avantageusement inférieure à 5. The second group of polymers that can be used according to the invention are polymers which correspond to the general formula (I)

in lacuelle
R 1 R 3 R 4 R 5 R 5 R 6, which may be identical or different, represent polymers chosen from homopolymers ethylene oxide, linear or branched alkylene oxide containing from 3 to 6 carbon atoms and linear or branched block copolymers ethylene oxide alkylene
n, m and p are integers equal to or greater than 0 and equal to or less than 10 (O <n × 10) and preferably of which the sum n + m. p is less than 20 and advantageously less than 5.

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

 The alkylene oxide groups are preferably chosen from propylene oxide and butylene oxide.

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

 Some of these polymers are marketed under the name TETRONIC.

 They are used in the same way as the PLURONICS as a soil removal agent but they have never been used for their anti-sequestering property.

dans laquelle
- R7, R3 identiques ou différents représentent un groupe méthyle ou des polymères choisis parmi les homopolymères oxyde d'éthylène, oxyde d'alkylène linéaire ou ramifié contenant notamment de 3 à 6 atomes de carbone et les copolymères blocs linéaires ou ramifiés oxyde d'éthylène - oxyde d'alkylène.The third group of polymers which can be used according to the invention are polymers which correspond to the general formula (II)

in which
R 7, R 3, which are identical or different, represent a methyl group or polymers chosen from homopolymers ethylene oxide, linear or branched alkylene oxide containing in particular from 3 to 6 carbon atoms and linear or branched block copolymers ethylene oxide - alkylene oxide.

- a is an integer between 1 and 150
at least one silicon atom carries a group chosen from
R7 and R8.

The polymers of formula (II) marketed are prepared in a manner known per se, for example described in the patent
US 2,970,150 Example 16.

dans laquelle
- R9, R10 identiques ou différents représentent des polymères coisis parmi les homopolymères oxyde d'éthylène, oxyde d'alkylène linéaire ou ramifié contenant notamment de 3 à 6 atomes de carbone et les copolymères blocs linéaires ou ramifiés oxyde d'éthylène oxyde d'alkylène chacun des groupes Rg R10 pouvant être différent d'un motif à l'autre.The fourth group of polymers that can be used according to the invention are polymers consisting of a chain of units corresponding to the general formula (III)

in which
R 9, R 10, which are identical or different, represent polymers chosen from homopolymers ethylene oxide, linear or branched alkylene oxide containing in particular from 3 to 6 carbon atoms and linear or branched block copolymers ethylene oxide alkylene oxide each of the groups Rg R10 may be different from one pattern to another.

 - A represents an optionally substituted alkylene or phenylene radical.

 The alkylene oxides are chosen in particular from propylene oxides.

 Among the polymers of formula (III), mention may be made of those for which A represents a hexamethylene, toluylene, isophorone, diphenylalkane or cyclohexamediyl radical.

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

 According to the invention, it is preferred to use, among the polymers of group 4, those which have: a molecular mass of between 4,000 and 40,000 and most particularly between 4,000 and 25,000, an amount by weight of ethylene oxide of between 40 and 50 Z, a sequence of ethylene oxides with a molecular weight of less than 3500 and even more preferentially of between 550 and 1600 and a sequence of alkylene oxides with a molecular mass of less than 4000 and preferably between 500 and 2,000.

 The polymers of formula (III) are obtained, for example, by the addition of ethylene oxide, alkylene oxide or ethylene oxide-alkylene oxide copolymers as defined in the first group of polymers according to US Pat. with diisocyanates selected from hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, di (isocyanatophenyl) alkanes in an anhydrous medium in the presence of tin salt.

 Polymers obtained by condensation of homopolymers with diisocyanates have substantially improved antiredéposant properties.

 The polymers previously described are used according to the invention as an antiredeposition agent when they lower the zeta potential of the textile fiber relative to the zeta potential of the bare fiber to a value less than or equal to 0.5. This decrease in zeta potential is a function of the amount of adsorbed polymer. This amount should preferably be greater than 0.02 mg / g.

 The adsorbed quantity is measured by contacting a tissue sample made of polymeric, organic, synthetic material (TERGAL type) with a mass of about 3.5 g fixed on a metal support with 100 ml of a NaCl solution (3). g / l) containing the polymer in a thermostatically controlled cell at 25 ° C. The medium is stirred.

When the adsorption equilibrium is reached, the adsorbed quantity is determined by an assay of the polymer concentration 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 polymer and after contact.

 The zeta potential or electrokinetic potential measurements are carried out by the flow potential method: a solution of NaCl 3 g / l (pH = 7), which may or may not contain the polymer, circulates under the effect of a pressure across a buffer consisting of several overlapping 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 measurement of the electrokinetic potential, the washers are contacted for 24 hours with a polymer solution in NaCl 3 g / l, so as to adsorb the polymer on the fibers. After this adsorption phase, the tissue washers are placed in the filter of the apparatus and the polymer solution used during the adsorption period is circulated by pressure through the tissue buffer.

 The procedure is the same with washers of non-polymer impregnated fabric.

 The antiredepositing effect of the polymer can be measured by a series of different tests in the presence of soiling.

 It is not obvious from the prior art to relate the effectiveness of the polymer and its anti-redepositing effect to the zeta potential of the fiber in polymeric, organic, synthetic material on which the polymer is adsorbed.

 It has been discovered by the present invention that the antiredeposing effect was achieved when the zeta potential of the fiber on which the polymer is adsorbed relative to the zeta potential of the bare fiber is less than or equal to 0.5.

 This zeta potential value is reached for minimal amounts of adsorbed polymer of 0.02 mg / g of tissue. This minimum amount varies with the type of adsorbed polymer.

 For the polymers of the first group consisting of ethylene oxide-alkylene oxide copolymers, the preferred amount of adsorbed polymer is between 0.1 and 5 mg / g of tissue.

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

 For the polymers of the third group corresponding to the general formula (II), the preferred amount of adsorbed polymer is greater than about 0.3 mg / g and even more preferably between 0.4 and 5 mg / g of tissue.

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

 The invention will now be more fully described without however limiting its scope, using the antiredeposition tests used and the examples that follow.

Antiredeposition tests used
Test nO 1
In a thermostated cell at 250 ° C. containing 100 ml of a solution of NaCl (3 g / l) and a concentration of 50 mg / l of anti-redepositing agent, 5 ml of a suspension of carbon black (black "PRINTEX U ", concentration 200 mg / l) previously dispersed with ultrasound and a tissue sample (TERGAL type polyester, m - 0.5 g) fixed on a metal support. The agitation of the medium is ensured by a bar magnet.

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

The deposition on the textile fibers is evaluated by the AR reflectance difference of the fabric ("ELREPHO" photometer).
ZEISS, filter ne10).

 The higher a R, the greater the deposition.

Test n 2
The antiredepositing efficacy of an additive is evaluated by performing five cumulative wash cycles in "Terg-O-Tometer" (United
States Testing Company Inc. Hobokin, NJ) in the presence of complete soiling ".

 Each cycle consists of a washing phase of 20 minutes (1 1 of solution per pot, T = 600C) 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 320 H.T.

The dirt used is of the type "Spangler (WG SPANGLER,
HD CROSS and BR SCHAAFSMA, J. Am. Oil Chemist's Soc. 42 (1965), 723), it is constituted by
100 g Sebum
4 g Oleic acid
8 g Triethanolamine
4 g Particulate soiling
884 g Water
The composition of the sebum is the following
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 Z Fine Paraffin 52/54
15 Z White whale
5 Z Cholesterol
The composition of particulate soil is as follows
86% Kaolin
8% Black smoke
4% Black Iron Oxide
2 Z Yellow iron oxide.

 The total concentration of soiling used is 50 g / l for each wash cycle.

The concentration of laundry used is 6 g / l, its composition will be weighted as follows
7.5% linear sodium alkylbenzene sulphonate
Sodium stearate 3 Z
C18 linear alcohol ethoxylated with 12 moles
of ethylene oxide 3 Z
Linear alcohol C18 ethoxylated with 50 moles
2% ethylene oxide
Sodium tripolyphosphate 27.5 Z
Sodium Pyrophosphate Anhydrous 2 Z
Trisodium phosphate anhydrous 0.5%
Silicate powder 3 Na 8.6 Z
Carboxymethylcellulose: Blanose BWS 1.5 Z
Tinopal SOPs 0.2 Z
Tinopal DMSX # 0.2%
Esperase NOVO # 0.3%
Perborate 25%
Magilex 120 # 1 Z
EDTA 0.2%
Sodium sulphate 17.5 Z
The fabric samples used in our wash tests are samples of polyester (11DACRON 54 "from
TESTFABRIC) previously washed at 60 C in a machine fed with fresh water and in the absence of detergent. Each pot of "Terg-O-Tometer" contains 6 rectangles of fabric (10 x 12 cm).

 The concentration of anti-redepositing additive used is 50 mg / l. The redeposition is quantified by the difference # R (measured by a GARDNER # photometer, filter Y) between the reflectance of the initially clean tissue and that of the tissue after five wash cycles. The anti-redepositing agent is all the more effective as # R is weak.

Test n 3
The experimental conditions used during this test are identical to those of the preceding test, with the difference that the soiling is no longer a liquid stain of the "Spangler" type, but a soiling impregnated on cotton samples ("WFK Testgewebe GmbH KREFELD "). Before each washing cycle, three rectangles (10 x 12 cm) of soiled cotton are introduced into each pot.

Example 1 to 11
Group 1 products
The value of the zeta / 4 potential of the fiber in the presence of
o polymers adsorbed with respect to the zeta potential of the bare fiber was measured according to the zeta potential measurement test in the presence of a polymer concentration in the solution of 10 mg / l. The amounts of polymer adsorbed per gram of tissue were measured under the same conditions (10 mg / l of polymer).

 Table 1 gives the results of the antiredepositant effect (E R) measured according to test 1 of products marketed under the Pluronics brand. The products decreasing the zeta potential to a value of less than 0.50 (Examples 1, 2, 3, 5) have a substantially improved antiredéposant effect compared with those whose potential does not meet the criteria of the invention, but some of which nevertheless have an excellent soil removal effect (eg 7).

Examples 12 to 19
Group 2 products
The value of the zeta potential, the amount adsorbed and the antiredeposing effect were determined as in the previous examples.

 Examples 12 to 17 were carried out with products consisting of ethylenes diamines ethoxypropyl, produced according to the general formula (I) in which n = 1, m = p = 0 and R1 R2 R4 R6 = (C3H60) X (C2H40) These products are sold under the name tetronic. Tests 12, 13, 16 and 17 are in accordance with the invention.

Example 18 was carried out on a product corresponding to the general formula (I) in which n = 1, m = p = O, R1 = R2 = R4 =
R6 = (C, H60) X (C2H40) y H and marketed under the name
LUTENSOL; it is in accordance with the invention.

 Example 19 was carried out on an ethoxypropyl triethylenetetramine, product corresponding to the general formula (I) in which n = m = p = 1, R1 = R2 = R4 = R6 = (C3H6) x (2; the invention.

 Tests 12 to 19 are reported in Table 2.

Example 20
Group 3 product
The value of the zeta potential, the amount of adsorbed polymer and the antiredéposant effect were determined as in the previous examples.

 Example 20 was carried out on a product of the general formula (II) wherein a = 12 and wherein four homopolymers of ethylene oxide of molecular weight 550 were fixed.

 Test 20 is reported in Table 3.

Examples 21 to 60
Group 4 products
The value of the zeta potential and the amount of adsorbed polymer were determined as in the previous examples.

 Examples 21 to 34 were carried out on polymers obtained by condensation of group 1 products using hexamethylene diisocyanate (HDI). These products were obtained by condensation of PLURONICS and hexamethylene diisocyanate at a temperature between 80 and 1050C in the presence of a catalyst such as dibutyltin dilaurate. Tests 21 to 34 are reported in Table 4a.

 Examples 35 to 60 were carried out on polymers obtained by condensation of ethylene oxide and alkylene oxide in the presence of hexamethylene diisocyanate. Tests 35 to 60 are reported in Table 4b, 4c and 4d.

TABLE 1

Mass <SEP> of <SEP> oxide <SEP>% <SEP> oxide <SEP> Mass <SEP> Test <SEP> of anti- <SEP> Quantity
<tb> Examples <SEP> PLURONICS # <SEP> of <SEP> propylene <SEP> of ethylene <SEP> molecular <SEP> redeposition <SEP>#R<SEP># / # o <SEP> adsorbed
<tb> mg / g
<tb> 1 <SEP> F <SEP> 108 <SEP> 3 <SEP> 250 <SEP> 80 <SEP> 16 <SEP> 200 <SEP> 1 <SEP> 3.9 <SEP> 0.11 <SEP > 0.17
<tb> 2 <SEP> F <SEP> 88 <SEP> 2 <SEP> 250 <SEP> 80 <SEP> 11 <SEP> 200 <SEP> 1 <SEP> 7.8 <SEW> 0.28 <SE > 0.12
<tb> 3 <SEP> F <SEP> 68 <SEP> 1 <SEP> 750 <SEP> 80 <SEP> 8 <SEP> 700 <SEP> 1 <SEP> 15.8 <SEP> 0.43 <SEP > 0.03
<tb> 4 <SEP> F <SEP> 38 <SEP> 950 <SEP> 80 <SEP> 4 <SEP> 700 <SEP> 1 <SEP> 33.3 <SEP> 0.90 <SEP> 0.02
<tb> 5 <SEP> p <SEP> 105 <SEP> 3 <SEP> 250 <SEP> 50 <SEP> 6 <SEP> 500 <SEP> 1 <SEP> 8.4 <SEQ> 0.46 <SEP > 0.11
<tb> 6 <SEP> p <SEP> 103 <SEP> 3 <SEP> 250 <SEP> 30 <SEP> 4 <SEP> 600 <SEP> 1 <SEP> 13.2 <SEP> 0.55 <SEP > 0.20
<tb> 7 <SEP> L <SEP> 64 <SEP> 1 <SEP> 750 <SEP> 40 <SEP> 2 <SEP> 900 <SEP> 1 <SEP> 31.9 <SEP> 0.95 <SEP > 0.03
<tb> 8 <SEP> p <SEP> 85 <SEP> 2 <SEP> 250 <SEP> 50 <SEP> 4 <SEP> 500 <SEP> 1 <SEP> 21.9 <SEP> 0.58 <SEP > 0.08
<tb> 9 <SEP> p <SEP> 75 <SEP> 2 <SEP> 050 <SEP> 50 <SEP> 4 <SEP> 100 <SEP> 1 <SEP> 22.4 <SEP> 0.63 <SEP > 0.07
<tb> 10 <SEP> L <SEP> 42 <SEP> 1 <SEP> 200 <SEP> 20 <SEP> 1 <SEP> 500 <SEP> 1 <SEP> 38.9 <SEP> 0.97 <SEP > 0.03
<tb> 11 <SEP> without <SEP> additive <SEP> 1 <SEP> 40 <SEP> 1 <SEP> 0
<tb> TABLE 2

Mass <SEP> of <SEP> oxide <SEP>% <SEP> oxide <SEP> Mass <SEP> Test <SEP> of anti- <SEP> Quantity
<tb> Examples <SEP> Products <SEP> of <SEP> propylene <SEP> of ethylene <SEP> molecular <SEP> redeposition <SEP>#<SEP> R <SEP># / # <SEP> o <SEP > adsorbed
<tb> used <SEP> mg / g
<tb> 11 <SEP> without <SEP> additive <SEP> 1 <SEP> 40 <SEP> 1 <SEP> 0
<tb> 12 <SEP> TETRONIC <SEP> 1301 <SEP> 5 <SEP> 750 <SEP> 10 <SEP> 6 <SEP> 400 <SEP> 1 <SEP> 10 <SEP> 0.31 <SEP> 0 15
<tb> 13 <SEP> TETRONIC <SEP> 1302 <SEP> 5 <SEP> 750 <SEP> 20 <SEP> 7 <SEP> 200 <SEP> 1 <SEP> 9.3 <SEW> 0.27 <SEP > 0.17
<tb> 14 <SEP> TETRONIC <SEP> 701 <SEP> 2 <SEP> 750 <SEP> 10 <SEP> 3 <SEP> 000 <SEP> 1 <SEP> 40 <SEP> 0.95 <SEP> 0 01
<tb> 15 <SEP> TETRONIC <SEP> 704 <SEP> 2 <SEP> 750 <SEP> 40 <SEP> 4 <SEP> 600 <SEP> 1 <SEP> 38.4 <SEP> 0.88 <SEP > 0.02
<tb> 16 <SEP> TETRONIC <SEP> 904 <SEP> 3 <SEP> 750 <SEP> 40 <SEP> 6 <SEP> 200 <SEP> 1 <SEP> 17.2 <SEP> 0.44 <SEP > 0.12
<tb> 17 <SEP> TETRONIC <SEP> 908 <SEP> 3 <SEP> 750 <SEP> 80 <SEP> 18 <SEP> 700 <SEP> 1 <SEP> 6.1 <SEP> 0.22 <SEP > 0.15
<tb> 18 <SEP> LUTENSOL <SE> ED <SEP> 370 <SEP> 3 <SEP> 000 <SEP> 70 <SEP> 10 <SEP> 000 <SEP> 1 <SEP> 12.6 <SEP> 0 , 30 <SEP> 0.13
<tb> 19 <SEP> Triethylene
<tb> tetramine <SEP> 5 <SEP> 000 <SEP> 80 <SEP> 25 <SEP> 000 <SEP> 1 <SEP> 2,3 <SEP> 0.37 <SEP> 0.08
<tb> ethoxypropylated
<tb> TABLE 3

<SEP>% <SEP> of oxide <SEP> Mass <SEP> Test <SEP> of anti- <SEP> Quantity
<tb> Example <SEP> Product <SEP> of ethylene <SEP> molecular <SEP> redeposition <SEP>#<SEP> R <SEP># / # <SEP> o <SEP> adsorbed
<tb> used <SEP> mg / g
<tb> 20 <SEP> Polysiloxane <SEP> 70 <SEP> 3 <SEP> 000 <SEP> 1 <SEP> 15.1 <SEP> 0.4 <SEP> 0.44
<tb> TABLE 4a

Products <SEP>% <SEP> oxide <SEP> Test <SEP> of anti- <SEP> Quantity
<tb> Examples <SEP> Group <SEP> 1 <SEP> Mass <SEP> of <SEP> HDI <SEP> of ethylene <SEP> redeposition <SEP>#R<SEP># / # <SEP> o <MS> adsorbed
<tb> mg / g
<tb> 21 <SEP> without <SEP> additive <SEP> 2 <SEP> 46 <SEP> 1 <SEP> 0
<tb> 22 <SEP> without <SEP> additive <SEP> 3 <SEP> 30 <SEP> 1 <SEP> 0
<tb> 23 <SEP> F <SEP> 108 <SEP> 5 <SEP> 80 <SEP> 2 <SEP> 29 <SEP> 0.23 <SEP> 0.15
<tb> 24 <SEP> F <SEP> 108 <SEP> 7 <SEP> 80 <SEP> 2 <SEP> 26 <SEP> 0.10 <SEP> 0.20
<tb> 25 <SEP> F <SEP> 108 <SEP> 5 <SEP> 80 <SEP> 3 <SEP> 16.3 <SEP> 0.23 <SEP> 0.15
<tb> 26 <SEP> F <SEP> 108 <SEP> 7 <SEP> 80 <SEP> 3 <SEP> 6.4 <SEP> 0.10 <SEP> 0.20
<tb> 27 <SEP> F <SEP> 68 <SEP> 5 <SEP> 80 <SEP> 2 <SEP> 41 <SEP> 0.40 <SEP> 0.07
<tb> 28 <SEP> F <SEP> 68 <SEP> 7 <SEP> 80 <SEP> 2 <SEP> 42 <SEP> 0.45 <SEP> 0.05
<tb> 29 <SEP> F <SEP> 68 <SEP> 5 <SEP> 80 <SEP> 3 <SEP> 10.6 <SEP> 0.40 <SEP> 0.07
<tb> 30 <SEP> F <SEP> 68 <SEP> 7 <SEP> 80 <SEP> 3 <SEP> 8 <SEP> 0.45 <SEP> 0.05
<tb> 31 <SEP> p <SEP> 103 <SEP> 10 <SEP> 30 <SEP> 2 <SEP> 28 <SEP> 0.18 <SEP> 0.32
<tb> 32 <SEP> p <SEP> 103 <SEP> 17 <SEP> 30 <SEP> 2 <SEP> 27 <SEP> 0.25 <SEP> 0.28
<tb> 33 <SEP> p <SEP> 103 <SEP> 10 <SEP> 30 <SEP> 3 <SEP> 4 <SEP> 0.18 <SEP> 0.32
<tb> 34 <SEP> p <SEP> 103 <SEP> 17 <SEP> 30 <SEP> 3 <SEP> 10.5 <SEP> 0.25 <SEP> 0.28
<tb> TABLE 4b

Products <SEP>% <SEP> oxide <SEP> Mass <SEP> Quantity
<tb> EX <SEP> mass <SEP> oxide <SEP> mass <SEP> oxide <SEP> mass <SEP> of ethylene <SEP> molecul. <SEP> Test <SEP>#R<SEP># / # o <SEP> adsorbed
<tb> ethylene <SEP> of <SEP> propylene <SEP> HDI <SEP> mg / g
<tb> 35 <SEP> PEG (600) 60g <SEP> PEG (1500) 150g <SEP> PPG (1000) 50g <SEP> 37.8 <SEP> 70 <SEP> 12 <SEP> 000 <SEP> 2 <SEP> 27 <SEP> 0.32 <SEP> 0.09
<tb> 3 <SEP> 14.3
<tb> 36 <SEP> PEG (600) 30g <SEP> PEG (3400) 170g <SEP> PPG (1000) 50g <SEP> 22.7 <SEP> 73 <SEP> 18 <SEP> 000 <SEP> 2 <SEP> 29 <SEP> 0.39 <SEP> 0.08
<tb> 3 <SEP> 18.2
<tb> 37 <SEP> PEG (8000) 160g <SEP> PPG (1000) 40g <SEP> 9.1 <SEP> 76 <SEP> 40 <SEP> 000 <SEP> 2 <SEP> 30 <SEP> 0 , 34 <SEP> 0.12
<tb> 3 <SEP> 11.5
<tb> 38 <SEP> PEG (8000) 160g <SEP> PPG (2000) 40g <SEP> 6.1 <SEP> 78 <SEP> 50 <SEP> 000 <SEP> 2 <SEP> 42 <SEP> 0 , 41 <SEP> 0.15
<tb> 3 <SEP> 13.3
<tb> 39 <SEP> PEG (600) 120g <SEP> PPG (1000) 100g <SEP> 45.4 <SEP> 45 <SEP> 9 <SEP> 000 <SEP> 2 <SEP> 32 <SEP> 0 , 10 <SEP> 0.32
<tb> 3 <SEP> 5.5
<tb> 40 <SEP> PEG (600) 30g <SEP> PEG (1500) 75g <SEP> PPG (1000) 100g <SEP> 30.2 <SEP> 45 <SEP> 12 <SEP> 000 <SEP> 2 <SEP> 32 <SEP> 0.08 <SEP> 0.35
<tb> 3 <SEP> 2
<tb> 41 <SEP> PEG (1500) 150g <SEP> PPG (1000) 50g <SEP> 30.2 <SEP> 45 <SEP> 17 <SEP> 000 <SEP> 3 <SEP> 5 <SEP> 0 , 09 <SEP> 0.30
<tb> PPG (2000) 100g
<tb> 42 <SEP> PEG (600) 18g <SEP> PEG (3400) 102g <SEP> PPG (2000) 120g <SEP> 18.1 <SEP> 46 <SEP> 25 <SEP> 000 <SEP> 3 <SEP> 5.2 <SEP> 0.12 <SEP> 0.28
<tb> 43 <SEP> PEG (600) 18g <SEP> PEG (3400) 102g <SEP> PPG (4000) 120g <SEP> 13.6 <SEP> 47 <SEP> 29 <SEP> 000 <SEP> 3 <SEP> 9 <SEP> 0.24 <SEP> 0.25
<tb> 44 <SEP> PEG (3400) 102g <SEP> PPG (4000) 120g <SEP> 9.1 <SEP> 44 <SEP> 40 <SEP> 000 <SEP> 3 <SEP> 16.8 <SEP > 0.40 <SEP> 0.18
<tb> 45 <SEP> PEG (8000) 160g <SEP> PPG (4000) 160g <SEP> 9.1 <SEP> 49 <SEP> 57 <SEP> 000 <SEP> 3 <SEP> 12.7 <SEP > 0.35 <SEP> 0.22
<tb> 46 <SEP> PEG (600) 60g <SEP> PEG (1500) 150g <SEP> PPG (1000) 100g <SEP> 45.4 <SEP> 60 <SEP> 12 <SEP> 000 <SEP> 2 <SEP> 32 <SEP> 0.18 <SEP> 0.20
<tb> 3 <SEP> 7.8
<tb> TABLE 4c

Products <SEP>% <SEP> oxide <SEP> Mass <SEP> Quantity
<tb> EX <SEP> mass <SEP> oxide <SEP> mass <SEP> oxide <SEP> mass <SEP> of ethylene <SEP> molecul. <SEP> Test <SEP>#R<SEP># / # o <SEP> adsorbed
<tb> ethylene <SEP> of <SEP> propylene <SEP> HDI <SEP> mg / g
<tb> 47 <SEP> PEG (1500) 150g <SEP> PPG (1000) 75g <SEP> 26.5 <SEP> 60 <SEP> 14 <SEP> 000 <SEP> 2 <SEP> 32 <SEP> 0 , 25 <SEP> 0.22
<tb> 3 <SEP> 10
<tb> 48 <SEP> PEG (600) 30g <SEP> PEG (3400) 170g <SEP> PPG (2000) 100g <SEP> 22.7 <SEP> 62 <SEP> 22 <SEP> 000 <SEP> 2 <SEP> 36 <SEP> 0.23 <SEP> 0.19
<tb> 3 <SEP> 11.7
<tb> 49 <SEP> PEG (3400) 170g <SEP> PPG (2000) 85g <SEP> 14.0 <SEP> 63 <SEP> 29 <SEP> 000 <SEP> 2 <SEP> 36 <SEP> 0 , 24 <SEP> 0.18
<tb> 3 <SEP> 18
<tb> 50 <SEP> PEG (8000) 160g <SEP> PPG (2000) 80g <SEP> 9.1 <SEP> 64 <SEP> 40 <SEP> 000 <SEP> 2 <SEP> 36 <SEP> 0 , 14 <SEP> 0.25
<tb> 3 <SEP> 8.5
<tb> 51 <SEP> PEG (8000) 160g <SEP> PPG (4000) 80g <SEP> 6.1 <SEP> 65 <SEP> 57 <SEP> 000 <SEP> 2 <SEP> 31 <SEP> 0 , 30 <SEP> 0.15
<tb> 3 <SEP> 14.5
<tb> PEG = polyethylene glycol
PPG = polypropylene glycol TABLE 4d

Products <SEP>% <SEP> oxide <SEP> Mass <SEP> Quantity
<tb> EX <SEP> mass <SEP> oxide <SEP> mass <SEP> oxide <SEP> mass <SEP> of ethylene <SEP> molecul. <SEP> Test <SEP>#R<SEP># / # o <SEP> adsorbed
<tb> ethylene <SEP> of <SEP> butylene <SEP> HDI <SEP> mg / g
<tb> 52 <SEP> PEG (600) 60g <SEP> PEG (1500) 150g <SEP> PTHF (1000) 50g <SEP> 37.8 <SEP> 70 <SEP> 12 <SEP> 000 <SEP> 2 <SEP> 28 <SEP> 0.20 <SEP> 0.12
<tb> 3 <SEP> 10
<tb> 53 <SEP> PEG (600) 30g <SEP> PEG (3400) 170g <SEP> PTHF (1000) 50g <SEP> 22.7 <SEP> 73 <SEP> 18 <SEP> 000 <SEP> 2 <SEP> 28 <SEP> 0.12 <SEP> 0.08
<tb> 3 <SEP> 18.3
<tb> 54 <SEP> PEG (8000) 160g <SEP> PTHF (1000) 40g <SEP> 9.1 <SEP> 76 <SEP> 40 <SEP> 000 <SEP> 3 <SEP> 7.8 <SEP > 0.17 <SEP> 0.09
<tb> 55 <SEP> PEG (600) 120g <SEP> PTHF (1000) 100g <SEP> 45.4 <SEP> 45 <SEP> 9 <SEP> 000 <SEP> 2 <SEP> 34 <SEP> 0 , 18 <SEP> 0.30
<tb> 3 <SEP> 4
<tb> 56 <SEP> PEG (600) 30g <SEP> PEG (1500) 75g <SEP> PTHF (1000) 100g <SEP> 30.2 <SEP> 45 <SEP> 12 <SEP> 000 <SEP> 2 <SEP> 34 <SEP> 0.12 <SEP> 0.35
<tb> 3 <SEP> 1
<tb> 57 <SEP> PEG (8000) 160g <SEP> PTHF (1000) 160g <SEP> 27.2 <SEP> 46 <SEP> 18 <SEP> 000 <SEP> 2 <SEP> 26 <SEP> 0 , 22 <SEP> 0.34
<tb> 3 <SEP> 11
<tb> 58 <SEP> PEG (600) 60g <SEP> PEG (1500) 150g <SEP> PTHF (1000) 100g <SEP> 45.4 <SEP> 59 <SEP> 12 <SEP> 000 <SEP> 2 <SEP> 29 <SEP> 0.21 <SEP> 0.28
<tb> 3 <SEP> 8.2
<tb> 59 <SEP> PEG (600) 30g <SEP> PEG (3400) 170g <SEP> PTHF (1000) 100g <SEP> 30.2 <SEP> 61 <SEP> 17 <SEP> 000 <SEP> 3 <SEP> 9.1 <SEP> 0.25 <SEP> 0.22
<tb> 60 <SEP> PEG (8000) 160g <SEP> PTHF (1000) 80g <SEP> 15.1 <SEP> 63 <SEP> 24 <SEP> 000 <SEP> 2 <SEP> 34 <SEP> 0 , 33 <SEP> 0.25
<tb> PTHF = polytetrahydrofuran

Claims (22)

 1. Detergent compositions characterized in that they contain at least one anti-redepositing polymer useful in particular for washing synthetic organic polymeric materials, which comprises at least one unit selected from the group ethylene oxide, alkylene oxide and which gives the fiber has a potential value zeta with respect to the zeta potential of the bare fiber less than or equal to 0.5 for a minimum amount of polymer adsorbed per serious tissue of 0.02 mg.  2. Compositions according to claim 1, characterized in that the polymer (s) has a molecular mass less than or equal to 150 OGO.  3. Compositions according to claim 2, characterized in that the polymer (s) has a molecular mass of between 2,000 and 150,000.  4. Compositions according to claim 3, characterized in that the polymer (s) has a molecular mass of between 4,000 and 100,000.  5. Compositions according to any one of the preceding claims, characterized in that the polymer (s) comprises a quantity by weight of ethylene oxide of between 10 and 90%.  6. Compositions according to claim 5, characterized in that -e (s) polymer (s) comprises an amount by weight of ethylene oxide between 30 and 90%.  ;. Compositions according to Claim 6, characterized in that the polymer (s) comprises an amount by weight of ethylene oxide of between 40 and 70%.  Compositions according to any one of the preceding claims, characterized in that the polymer (s) is composed of linear or grafted ethylene oxide - linear or grafted alkylene oxide blocks containing from 3 to 6 carbon atoms.  9. Compositions according to claim 8, characterized in that the (s) polymer (s) is composed of ethylene oxide - propylene oxide blocks.  10. Compositions according to any one of claims 1 to 7, characterized in that the (s) polymer (s) corresponds to the general formula (I).

in which  R 1 R 3 R 4 R 5 R 5 R 6, which may be identical or different, represent polymers chosen from homopolymers ethylene oxide, linear or branched alkylene oxide containing from 3 to 6 carbon atoms and linear or branched block copolymers ethylene oxide alkylene  - n m p are integers equal to or greater than 0 and equal to or less than 10 and whose sum n + m + p is less than 20.  11. Compositions according to claim 10 characterized in that in the general formula (I) the sum n + m + p is less than 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 polymer is composed of ethylene oxide blocks - propylene oxide or butylene.  14. Compositions according to one of claims 10 to 13 characterized in that in formula (I) the nitrogen atoms are quaternized.  15. Compositions according to any one of claims 1 to 7 characterized in that the (s) polymer (s) corresponds to the general formula (II)

 in which  - R7 R8 identical or different represent polymers selected from homopolymers ethylene oxide, linear or branched alkylene oxide containing from 3 to 6 carbon atoms and block polymers linear or branched ethylene oxide - alkylene oxide.  - a is an integer between 1 and 150.  - At least one silicon atom carries a group selected from R7 and R8.  16. Compositions according to any one of claims 1 to 7 characterized in that the polymers comprise at least one unit corresponding to the general formula (III)

 in which  - Rg R1o identical or different represent polymers chosen from homopolymers ethylene oxide, linear or branched alkylene oxide containing from 3 to 6 carbon atoms and linear or branched block copolymers ethylene oxide - alkylene oxide  - A represents an optionally substituted alkylene or phenylene radical.  17. Compositions according to claim 17, characterized in that the alkylene oxides are propylene oxides.  18. Compositions according to claims 16 to 17, characterized in that the polymers have a molecular weight of between 4000 and 25000.  19. Compositions according to claim 16 to 18, characterized in that the polymers comprise an amount by weight of ethylene oxide of between 40 and 50%.  20. Compositions according to claims 16 to 19 characterized in that the polymers comprise an ethylene oxide of tolecular mass less than 3500 and preferably between 550 and 1600.  21. Compositions according to claim 16 to 19, characterized in that the polymers comprise an alkylene oxide with a molecular mass of less than 4,000 and preferably of between 500 and 2,000.  22. Compositions according to any one of claims 8 to 9 characterized in that give the fiber a zeta potential value with respect to the potential of the bare fiber less than 0.5 for an amount of polymer adsorbed per gram of tissue included between 0.1 mg and 5 mg / g.  23. Compositions according to any one of claims 10 to 14 characterized in that they give the fiber a zeta potential value with respect to the potential of the bare fiber less than 0.5 for a quantity of polymer adsorbed per gram of tissue between 0.02 and 5 mg / g.  24. Compositions according to claim 15 characterized in that they give the fiber a potential value zeta with respect to the potential of the bare fiber less than 0.5 for an amount of adsorbed polymer per gram of tissue greater than about 0, 3 mg and preferably between 0.4 and 5 mg / g.  25. Compositions according to any one of claims 16 to 21 characterized in that they give the fiber a zeta potential value with respect to the potential of the bare fiber less than 0.5 for a quantity of adsorbed polymer between 0 , 05 and 5 mg / g.