Polymer as thickener and suspending agent

Abstract

The present invention relates to a polymer obtained by radical polymerization of a mixture of monomers comprising: at least one anionic monomer (a) having a polymerizable vinyl function; at least one non-ionic hydrophobic monomer (b) having a polymerizable vinyl function; and one or more crosslinking monomer(s) (c) including at least one compound of formula (I) in which R is a hydrogen atom or a methyl group, n is zero or an integer from 1 to 30, and R.sub.1 is a linear or branched C.sub.1-C.sub.20 alkylene group. The present invention also relates to a process for the preparation thereof by radical polymerization, to an aqueous composition comprising same, to the use thereof as a thickener and suspending agent and also to the use of a monomer of formula (I) for synthesizing a polymer.

Claims

1. A polymer obtained by radical polymerization of a mixture of monomers comprising: (a) at least one anionic monomer (a) having a polymerizable vinyl group; (b) at least one nonionic hydrophobic monomer (b) having a polymerizable vinyl group; and (c) at least one cross-linking monomer (c) comprising at least one compound of formula (I): ##STR00012## wherein: R is a hydrogen atom or a methyl group; n is 1; and R.sub.1 is a C.sub.1-C.sub.20 linear or branched alkyl group.

2. The polymer according to claim 1, wherein: R.sub.1 is a (CH.sub.2).sub.2 group.

3. The polymer according to claim 1, wherein the mixture of monomers further comprises: (d) at least one monomer (d) having a polymerizable vinyl group and an at least C.sub.10 hydrophobic hydrocarbon chain, the monomer (d) being distinct from the monomer (b).

4. The polymer according to claim 1, wherein the mixture of monomers further comprises: (e) at least one additional monomer (e) that is optionally nonionic, the additional monomer (e) being distinct from the monomer (b).

5. The polymer according to claim 1, wherein the at least one anionic monomer (a) is selected from the group consisting of acrylic acid, a salt of acrylic acid, methacrylic acid, a salt of methacrylic acid, and a mixture thereof.

6. The polymer according to claim 1, wherein the at least one anionic monomer (a) represents more than 20% by weight, based on a total weight of monomers forming the polymer.

7. The polymer according to claim 1, wherein the at least one nonionic hydrophobic monomer (b) is selected from the group consisting of a C.sub.1-C.sub.8 alkyl acrylate, a C.sub.1-C.sub.8 alkyl methacrylate, and a mixture thereof.

8. The polymer according to claim 1, wherein the at least one nonionic hydrophobic monomer (b) represents from 45% to 75% by weight, based on a total weight of monomers forming the polymer.

9. The polymer according to claim 1, wherein the mixture of monomers further comprises, as the cross-linking monomer (c), at least one monomer, which is different from the compound of formula W and selected from the group consisting of trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, ethylene glycol di(meth)acrylate, methylenebisacrylamide, triallylcyanurate, diallylphtalate, diallylmaleate, and a mixture thereof.

10. The polymer according to claim 1, wherein the at least one cross-linking monomer (c) represents less than 5% by weight, based on a total weight of monomers forming the polymer.

11. The polymer according to claim 3, wherein the at least one monomer (d) comprises a monomer of formula (II):
T-A-Z(II) wherein: T represents a polymerizable group allowing copolymerization of the monomer (d); A represents a polymeric chain comprising: m units of alkylene oxide of formula CH.sub.2CHR.sub.1O with R.sub.1 representing an alkyl group comprising from 1 to 4 carbons, and m varying from 0 to 150, p units of alkylene oxide of formula CH.sub.2CHR.sub.2O with R.sub.2 representing an alkyl group comprising from 1 to 4 carbons, and p varying from 0 to 150, n units of ethylene oxide with n varying from 0 to 150, in which the alkylene oxide units of formula CH.sub.2CHR.sub.1O, the alkylene oxide units of formula CH.sub.2CHR.sub.2O, and the ethylene oxide units are distributed in blocks, alternating or random; and Z represents a saturated or unsaturated, linear, branched, cyclic or polycyclic, fatty chain of at least 10 carbon atoms, optionally comprising at least one heteroatom.

12. The polymer according to claim 3, wherein the at least one monomer (d) represents from 0 to 20% by weight, based on a total weight of monomers forming the polymer.

13. The polymer according to claim 4, wherein the additional monomer (e) is selected from the group consisting of: 2-acrylamido-2-methylpropanesulfonic acid and a salt thereof, an unsaturated telomer of acrylic acid, a monomer of formula (e1): ##STR00013## wherein: R.sub.a, R.sub.b and R.sub.c represent, independently of one another, H or CH.sub.3, and n is an integer equal to 1 or to 2, and a monomer of formula (e2): ##STR00014## wherein: R.sub.a, R.sub.b, R.sub.c and R.sub.d represent, independently of one another, H or CH.sub.3, X represents (CO) or (CH.sub.2).sub.r with r=0, 1 or 2, (AO) represents a polyalkoxylated chain comprising alkoxylated units, distributed in blocks, alternating or random, selected from the group consisting of ethoxylated units EO, propoxylated units PO and butoxylated units BO, and q is equal to 0 or represents an integer varying from 1 to 150.

14. A method for preparing, by radical polymerization, the polymer of claim 1, the method comprising polymerizing a mixture of: the at least one anionic monomer (a), the at least one nonionic hydrophobic monomer (b), the at least one cross-linking monomer (c), optionally at least one monomer (d) having a polymerizable vinyl group and an at least C.sub.10 hydrophobic hydrocarbon chain, the at least one monomer (d) being distinct from the monomer (b), and optionally at least one additional monomer (e) that is optionally nonionic, the monomer (e) being distinct from the monomer (b).

15. The method according to claim 14, further comprising: polymerizing, in the presence of the polymer, a second mixture of monomers comprising: at least one anionic monomer (a) having a polymerizable vinyl group, at least one nonionic hydrophobic monomer (b) having a polymerizable vinyl group, at least one cross-linking monomer (c) comprising at least one compound of formula ##STR00015## wherein: R is a hydrogen atom or a methyl group, n is equal to 0 or is an integer from 1 to 30 and R.sub.1 is a C.sub.1-C.sub.20 linear or branched alkylene group, optionally at least one monomer (d) having a polymerizable vinyl group and an at least C.sub.10 hydrophobic hydrocarbon chain, the monomer (d) being distinct from the monomer (b), and optionally at least one additional monomer (e) that is optionally nonionic, the additional monomer (e) being distinct from the monomer (b), to obtain a second polymer.

16. An aqueous composition, comprising at least one polymer of claim 1.

17. A method, comprising polymerizing at least one monomer to obtain a polymer, wherein the at least one monomer comprises a compound of formula (I): ##STR00016## wherein: R is a hydrogen atom or a methyl group; n is 1; R.sub.1 is a C.sub.1-C.sub.20 linear or branched alkylene group; and an amount of the compound of formula (I) is less than 5% by weight, based on a total weight of the at least one monomer.

Description

EXAMPLES

(1) The following abbreviations are used:

(2) MAA: methacrylic acid

(3) EA: ethyl acrylate

(4) MA: monomer (d) of formula (III) in which m and p are equal to zero, n is equal to 25,

(5) R.sub.1 represents CH.sub.3, Z is a branched chain comprising 16 carbon atoms, namely 2-hexyldecanyl

(6) MA1: monomer (d) of formula (III) in which m and p are equal to zero, n is equal to 25, R.sub.1 represents CH.sub.3, Z is a branched chain comprising 32 carbon atoms, namely 2-tetradecyl-octadecanyl

(7) MA2: monomer (d) of formula (III) in which m and p are equal to zero, n is equal to 25, R.sub.1 represents CH.sub.3, Z is a linear chain comprising 22 carbon atoms, namely docosyl

(8) MA3: monomer (d) of formula (III) in which m and p are equal to zero, n is equal to 36, R.sub.1 represents CH.sub.3, Z is a branched chain comprising 20 carbon atoms, namely 2-octyldodecanyl

(9) MA4: monomer (d) of formula (III) in which m and p are equal to zero, n is equal to 30, R.sub.1 represents CH.sub.3, Z is an oxo chain comprising 12 carbon atoms

(10) FA-512AS (sold by the company Hitachi): ethylene glycol dicyclopentenyl ether acrylate (EGDCPEA)

(11) FA-512MT (sold by the company Hitachi): ethylene glycol dicyclopentenyl ether methacrylate (EGDCPEMA)

(12) FA-511AAS (sold by the company Hitachi): dicyclopentenyl ether acrylate (DCPEA)

(13) SR 351 (sold by the company Sartomer): trimethylolpropane triacrylate (TMPTA)

(14) SR 454 (sold by the company Sartomer): trimethylolpropane triacrylate 30E (TMPTA 30E)

(15) TMPDE 90 (sold by the company Perstorp): trimethylolpropane diallyl ether (TMPDAE)

(16) SR DFM (sold by the company Sartomer): monomethacrylic TMPDAE

(17) SIPOMER HPM100 (sold by the company Rhodia): nopol methacrylate 100E

(18) VISIOMER EGDMA SG (sold by the company Evonik): ethylene glycol dimethacrylate (EDMA).

(19) Example of Synthesis of Polymers in a Semi-Batch Method

(20) The protocol for synthesizing the polymer carried out in semi-batch mode is as follows: 432 g of deionized water and 9.29 g of a solution containing 28% by mass of sodium lauryl ether sulfate are placed in a stirred 1 L reactor heated with an oil bath.

(21) The premix comprising the following ingredients: ethyl acrylate: 196.1 g, methacrylic acid: 99.67 g, macromonomer noted as MA: 25.96 g, EGDCPEA: 1.38 g, deionized water: 172.5 g and solution containing 28% of sodium lauryl ether sulfate: 6.47 g is prepared in a beaker.

(22) This premix is stirred so as to form an emulsion.

(23) A solution consisting of 0.1167 g of sodium persulfate and 5 g of deionized water, known as initiator 1, is prepared.

(24) A solution consisting of 0.3 g of sodium persulfate and 50 g of deionized water, known as initiator 2, is prepared.

(25) Initiator 1 is injected when the reactor is heated to a temperature of 86 C.+2 C.

(26) Next, the solution of polymerization initiator 2 is injected into the reactor over 2 hours and the monomer premix is injected into the reactor over 2 hours, in parallel.

(27) 35 g of water are then added.

(28) The resulting mixture is heated for a further one hour at a temperature of 86 C.2 C.

(29) The whole is then cooled to room temperature.

(30) Example of Synthesis of Multiphasic Polymers

(31) The protocol for synthesizing the multiphasic polymer is as follows:

(32) 430 g of deionized water and 9.29 g of a solution containing 28% by mass of sodium lauryl ether sulfate are placed in a stirred 1 L reactor heated with an oil bath.

(33) The premix P1 comprising the following ingredients: ethyl acrylate: 131.74 g, methacrylic acid: 81.86 g, macromonomer noted as MA: 19.82 g, EGDCPEA: 1.05 g, deionized water: 139.1 g and solution containing 28% of sodium lauryl ether sulfate: 4.93 g is prepared in a beaker.

(34) This premix is stirred so as to form an emulsion.

(35) The premix P2 comprising the following ingredients: ethyl acrylate: 54.75 g, methacrylic acid: 26.74 g, macromonomer noted as MA: 6.14 g, EGDCPEA: 0.33 g, deionized water: 42.8 g and solution containing 28% of sodium lauryl ether sulfate: 1.54 g is prepared in a beaker.

(36) This premix is stirred so as to form an emulsion.

(37) A solution consisting of 0.318 g of sodium persulfate and 5 g of deionized water, known as initiator 1, is prepared.

(38) A solution consisting of 0.269 g of sodium persulfate and 50 g of deionized water, known as initiator 2, is prepared.

(39) Initiator 1 is injected when the reactor is heated to a temperature of 86 C.+2 C.

(40) Next, the solution of polymerization initiator 2 is injected into the reactor over 2 hours and, in parallel, the premix P1 of monomers is injected into the reactor over 90 minutes, followed by the premix P2 over 30 minutes.

(41) 35 g of water are then added.

(42) The resulting mixture is heated for a further 1 hour at a temperature of 86 C.+2 C.

(43) The whole is then cooled to room temperature.

(44) All the polymers presented in the examples that follow were synthesized under the conditions described above, varying the compositions of monomers in the monomer premixes.

(45) The composition of the polymer is indicated as a weight percentage of each of the monomers based on the total weight of monomers forming the polymer.

(46) Similarly, when it is a multiphasic polymer, the composition of the polymer P1 and, respectively, that of the polymer P2 is indicated as a weight percentage of each of the monomers based on the total weight of the monomers of P1 and, respectively, of P2.

(47) Evaluation in an Aqueous Formulation

(48) The polymers are tested in an aqueous formulation, having the composition indicated in table 1 below (2.4% or 3% by weight of polymer based on the total weight of the composition).

(49) TABLE-US-00001 TABLE 1 Compounds Amount (wt. %) Sodium lauryl ether sulfate (SLES) 9 Cocamidopropyl betaine (CAPB) 3 Test polymer 2.4 or 3 Water qsp 100

(50) The pH of the formulation is adjusted to a value of 5, 6 or 7 by adding lactic acid or sodium hydroxide.

(51) Properties Evaluated

(52) The compositions are evaluated for their clearness, viscosity and suspending performances properties.

(53) Clearness

(54) The clearness of the composition is evaluated by measuring the transmittance according to the following protocol:

(55) The measurements are taken on a Genesys 10 UV UV spectrometer (Cole Parmer), equipped with Rotilabo-Einmal Kuvetten PS, 4.5 mL cuvettes. In practice, the machine is preheated for 10 minutes before use. A first measurement is first taken using a cuvette filled with 3.8 mL of double-deionized water (the blank). The measurement is then taken with a cuvette filled with 3.8 mL of the solution of cosmetic composition to be tested. The transmittance is then measured at a wavelength of 500 nm. The higher the transmittance value, expressed as a percentage, the clearer the cosmetic composition.

(56) As indicated previously, it is considered that at a transmittance value at 500 nm of at least 60%, the composition is limpid.

(57) Viscosity

(58) The viscosity of said formulations is measured using a Brookfield, LVT model viscometer. Before measuring the viscosity, each of the formulations is left to stand for 24 hours at 25 C. The spindle must be centered relative to the aperture of the flask. The viscosity is then measured at 6 rpm (rotations per minute) using the appropriate module. The viscometer is left rotating until the viscosity is stable.

(59) The rheology modifying agent should give a sufficient viscosity to the formulation in which it is used. In general, the viscosity desired for the thickened formulations is greater than 4,000 mPa.Math.s, in particular greater than 6,000 mPa.Math.s and more particularly greater than 8,000 mPa.Math.s.

(60) Suspending Performances

(61) Viscoelasticity measurements are taken on said formulations using a Haake-Mars III rheometer. The Tan() and G variations as a function of the stress (sweep from 0 to 1000 dyn/cm.sup.2) are measured at 25 C. using 1 cone/plate geometry. The Tan() and G values at 10 dyn/cm.sup.2 are extrapolated and the elastic resistance value is deduced from this measurement.

(62) In general, the stability of particles introduced into said formulations is observed for combined values of G>60 Pa, Tan()<0.55 and elastic resistance >70 dyn/cm.sup.2.

Example 1: Polymers According to the Invention

(63) The polymers tested, named pol.1 to pol.20, illustrated in tables 2 to 6, are polymers according to the invention which were synthesized according to the protocols detailed above.

(64) More specifically, pol.1 to pol.14 are polymers prepared according to the semi-batch method, whereas the polymers pol.15 to pol.20 are multiphasic polymers.

(65) In particular, it should be noted that: pol. 1 and pol.2, given in table 2, are polymers not comprising any monomer (d), pol.3 to pol.9 and pol.15 to pol.20, given in tables 2, 3 and 5, are polymers comprising various cross-linking monomers (c) and pol.10 to pol.14, given in table 4, are polymers comprising various monomers (d).

(66) TABLE-US-00002 TABLE 2 Polymers tested Pol. 1 Pol. 2 Pol. 3 Pol. 4 Pol. 5 Overall EA 64.00 63.82 62.52 62.52 composition MAA 35.40 35.26 34.54 34.54 MA 2.04 2.04 Cross-linking 0.60 0.92 0.90 0.90 0.90 agent (c) EGDCPEA EGDCPEA EGDCPEA EGDCPEMA DCPEA 3% active G (Pa) 97 70 77 91 agent, pH = 7 Tan () 0.36 0.40 0.54 0.54 Elastic 110 80 110 120 115 resistance (dyn/cm.sup.2) T(500 nm) (%) 98 96 97 98 93 Brook. visco. 17500 8700 15400 19900 18200 (mPa .Math. s) 3% active Brook. visco. 25300 25700 29000 29000 28500 agent, pH = 6 (mPa .Math. s) 3% active Brook. visco. 12200 12300 16500 16500 17600 agent, pH = 5 (mPa .Math. s)

(67) TABLE-US-00003 TABLE 3 Polymers tested Pol. 6 Pol. 7 Pol. 8 Pol. 9 Overall EA 60.44 60.80 60.3 composition MAA 30.91 31.10 31.00 31.00 MA 7.80 7.80 7.80 7.80 Cross-linking 0.85 0.30 0.90 0.90 agent (c) EGDCPEA EGDCPEA EGDCPEA + EGDCPEA + TMPTA TMPTA 3OE (50/50) (50/50) 2.4% active G (Pa) 120 75 108 126 agent, pH = 6 Tan () 0.30 0.45 0.31 0.30 Elastic resistance 115 120 110 120 (dyn/cm.sup.2) T(500 nm) (%) 89 95 90 90 Brook. visco. 17400 16400 17400 19300 (mPa .Math. s) 2.4% active G (Pa) 107 66 105 109 agent, pH = 5 Tan () 0.30 0.44 0.31 0.30 Elastic resistance 110 90 110 110 (dyn/cm.sup.2) T(500 nm) (%) 85 93 87 87 Brook. visco. 15700 14000 15100 16300 (mPa .Math. s)

(68) TABLE-US-00004 TABLE 4 Polymers tested Pol. 10 Pol. 11 Pol. 12 Pol. 13 Pol. 14 Overall EA 60.67 60.67 60.67 60.67 60.67 composition MAA 31.10 31.10 31.10 31.10 31.10 Monomer (d) 7.80 7.80 7.80 7.80 7.80 MA MA1 MA2 MA3 MA4 EGDCPEA 0.43 0.43 0.43 0.43 2.4% active G (Pa) 119 109 100 173 92 agent, pH = 6 Tan () 0.33 0.30 0.40 0.42 0.26 Elastic resistance 150 110 110 300 100 (dyn/cm.sup.2) T(500 nm) (%) 93 80 94 91 91 Brook. visco. 19200 16000 21100 45100 12300 (mPa .Math. s) 2.4% active G (Pa) 97 81 96 149 65 agent, pH = 5 Tan () 0.34 0.26 0.34 0.33 0.29 Elastic resistance 130 85 105 220 80 (dyn/cm.sup.2) T(500 nm) (%) 91 66 91 83 86 Brook. visco. 16000 10300 17300 32700 9800 (mPa .Math. s)

(69) TABLE-US-00005 TABLE 5 Polymers tested Pol. 15 Pol. 16 Composition EA 60.34 60.17 P1 MAA 36.79 36.69 MA 2.17 2.17 Cross-linking 0.70 0.97 agent (c) EGDCPEA EGDCPEMA Composition EA 67.70 68.15 P2 MAA 29.20 29.40 MA 1.72 1.73 Cross-linking 1.38 0.72 agent (c) EGDCPEA EGDCPEMA Overall EA 62.52 62.52 composition MAA 34.54 34.54 MA 2.04 2.04 Cross-linking 0.90 0.90 agent (c) Proportion P1 70.40 70.60 Proportion P2 29.60 29.40 3% active G (Pa) 83 68 agent, pH = 7 Tan () 0.51 0.51 Elastic resistance 115 95 (dyn/cm.sup.2) T(500 nm) (%) 97 97 Brook. visco. 17100 20400 (mPa .Math. s) 3% active Brook. visco. 29700 29500 agent, pH = 6 (mPa .Math. s) 3% active Brook. visco. 13300 14600 agent, pH = 5 (mPa .Math. s)

(70) TABLE-US-00006 TABLE 6 Polymers tested Pol. 17 Pol. 18 Pol. 19 Pol. 20 Composition EA 55.92 56.16 55.92 55.92 P1 MAA 35.00 35.16 35.00 35.00 MA 8.19 8.23 8.19 8.19 Cross-linking 0.89 0.45 0.89 0.89 agent (c) EGDCPEA EGDCPEA EGDCPEMA DCPEA Composition EA 62.00 62.23 62.00 62.00 P2 MAA 30.50 30.61 30.50 30.50 MA 6.76 6.79 6.76 6.76 Cross-linking 0.74 0.38 0.74 0.74 agent (c) EGDCPEA EGDCPEA EGDCPEMA DCPEA Overall EA 57.58 57.82 57.58 57.58 composition MAA 33.77 33.92 33.77 33.77 MA 7.80 7.83 7.80 7.80 Cross-linking 0.85 0.43 0.85 0.85 agent (c) Proportion P1 72.74 72.72 72.74 72.74 Proportion P2 27.26 27.28 27.26 27.26 2.4% active G (Pa) 94 141 97 73 agent, pH = 6 Tan () 0.29 0.28 0.30 0.47 Elastic resistance 85 150 100 75 (dyn/cm.sup.2) T(500 nm) (%) 78 88 81 94 Brook. visco. 11800 19500 13200 8700 (mPa .Math. s) 2.4% active G (Pa) 140 139 144 121 agent, pH = 5 Tan () 0.25 0.25 0.24 0.25 Elastic resistance 120 150 130 120 (dyn/cm.sup.2) T(500 nm) (%) 69 80 69 65 Brook. visco. 14600 18700 15300 13500 (mPa .Math. s)

(71) The results presented in tables 2 to 6 show that the polymers according to the invention not only have good properties in terms of thickening, but also make it possible to obtain formulations that have good suspending performances and high clearness for all of the polymers tested.

(72) In addition, the results given in table 3 for pol.8 and pol.9 show that it is possible to use an additional cross-linking monomer (c), in the present case TMPTA or TMPTA 30E, in addition to a compound of formula (I), in the present case EGDCPEA.

Example 2: Polymers Outside the Invention

(73) The polymers tested, named C1 to C9, illustrated in tables 7 to 10, are polymers outside the invention which were synthesized according to the protocols detailed above and which comprise cross-linking monomers not in accordance with those used in the present invention. More particularly, the polymers C1 to C6 are polymers prepared according to the semi-batch method, whereas the polymers C7 to C9 are multiphasic polymers.

(74) TABLE-US-00007 TABLE 7 C1 C2 C3 outside the outside the outside the Polymers tested invention invention invention Overall EA 63.54 62.52 62.52 composition MAA 35.56 34.54 34.54 MA 2.04 2.04 Cross-linking 0.90 0.90 0.90 agent (c) TMPTA + TMPTA TMPTA + TMPDAE monomethacrylic (75/25) TMPDAE (63/37) 3% active G (Pa) 29 44 49 agent, Tan () 0.56 0.90 0.58 pH = 7 Elastic 30 55 40 resistance (dyn/cm.sup.2) T(500 nm) (%) 92 98 97 Brook. visco. 5100 14000 9100 (mPa .Math. s) 3% active Brook. visco. 23600 8800 24300 agent, (mPa .Math. s) pH = 6 3% active Brook. visco. 14500 5300 14400 agent, (mPa .Math. s) pH = 5

(75) TABLE-US-00008 TABLE 8 C4 C5 outside the outside the Polymers tested invention invention Overall EA 62.52 62.52 composition MAA 34.54 34.54 MA 2.04 2.04 Cross-linking 0.90 0.90 agent (c) 5-vinyl-2- nopol norbornene methacrylate 10 OE 3% active G (Pa) 52 55 agent, pH = 7 Tan () 1.23 1.88 Elastic resistance 40 120 (dyn/cm.sup.2) T(500 nm) (%) 95 99 Brook. visco. 3800 20100 (mPa .Math. s) 3% active Brook. visco. 8220 1530 agent, pH = 6 (mPa .Math. s) 3% active Brook. visco. 4880 2970 agent, pH = 5 (mPa .Math. s)

(76) TABLE-US-00009 TABLE 9 C6 outside the Polymers tested invention Overall EA 60.44 composition MAA 30.91 MA 7.80 Cross-linking 0.85 agent (c) TMPTA 2.4% active G (Pa) 42 agent, pH = 6 Tan () 0.58 Elastic resistance 50 (dyn/cm.sup.2) T(500 nm) (%) 94 Brook. visco. 12400 (mPa .Math. s) 2.4% active G (Pa) 32 agent, pH = 5 Tan () 0.58 Elastic resistance 40 (dyn/cm.sup.2) T(500 nm) (%) 92 Brook. visco. 10800 (mPa .Math. s)

(77) TABLE-US-00010 TABLE 10 C7 C8 C9 outside the outside the outside the Polymers tested invention invention invention Composition EA 55.92 55.92 55.92 P1 MAA 35.00 35.00 35.00 MA 8.19 8.19 8.19 Cross-linking 0.89 0.89 0.89 agent (c) EDMA Tricyclodecane 5-vinyl-2- dimethanol norbornene dimethacrylate Composition EA 62.00 62.00 62.00 P2 MAA 30.50 30.50 30.50 MA 6.76 6.76 6.76 Cross-linking 0.74 0.74 0.74 agent (c) EDMA Tricyclodecane 5-vinyl-2- dimethanol norbornene dimethacrylate Overall EA 57.58 57.58 57.58 composition MAA 33.77 33.77 33.77 MA 7.80 7.80 7.80 Cross-linking 0.85 0.85 0.85 agent (c) EDMA Tricyclodecane 5-vinyl-2- dimethanol norbornene dimethacrylate Proportion P1 72.74 72.74 72.74 Proportion P2 27.26 27.26 27.26 2.4% active G (Pa) 28 26 Not agent, determinable pH = 6 Tan () 0.71 0.78 Not determinable Elastic 40 40 Not resistance determinable (dyn/cm.sup.2) T(500 nm) (%) 95 97 55 Brook. visco. 7900 8100 1100 (mPa .Math. s) 2.4% active G (Pa) 28 25 Not agent, determinable pH = 5 Tan () 0.65 0.68 Not determinable Elastic 40 35 Not resistance determinable (dyn/cm.sup.2) T(500 nm) (%) 94 95 45 Brook. visco. 9000 8700 3100 (mPa .Math. s)

(78) In general, the results given in tables 7 to 10 show that the properties of the polymers (thickening effect, suspending performances and clearness) vary according to the nature of the cross-linking monomer used not compliant with the invention.

(79) Certain comparisons, by way of example, are illustrated in the following section.

(80) For example, by comparing compliant pol.6 (EGDCPEA) and non-compliant C6 (TMPTA), it is observed that the formulation comprising pol.6 has better suspending properties (significantly higher G value and lower Tan () value), a clearness of the same order of magnitude and viscosity values that are higher overall than a formulation comprising C6 or TMPTA.

(81) By comparing compliant pol.2 (EGDCPEA) and non-compliant C1 (TMPTA+TMPDAE (75/25)), it is observed that the formulation comprising pol.2 has better suspending properties, and also a clearness and viscosity values of the same order of magnitude at pH 6 and 5 compared to a formulation comprising C1 or TMPTA/TMPDAE.

(82) By comparing compliant pol.3, pol.4, pol.5, pol.15 or pol.16 with non-compliant C2 or C3, it is observed that the formulations comprising the compliant polymers have better suspending properties and a clearness of the same order of magnitude.

(83) By comparing compliant pol.3, pol.4, pol.5, pol.15 or pol.16 with non-compliant C4, it is observed that the formulations comprising the compliant polymers have higher viscosity values.

(84) By comparing compliant pol.17, pol.19 or pol.20 with non-compliant C7 or C8, it is observed that the formulations comprising the compliant polymers have better suspending properties, a higher viscosity and a clearness of the same order of magnitude.

(85) Finally, by comparing compliant pol.17, pol.19 or pol.20 with non-compliant C9, it is observed that the formulations comprising the compliant polymers have better clearness and a higher viscosity.

Example 3: Ultra-Mild Scrubbing Shower Gel

(86) This example illustrates the use of agents according to the invention in cosmetic formulations of ultra-mild shower gel type, and serves to demonstrate the rheological properties (suspension and viscosity) and organoleptic properties afforded according to the invention.

(87) Thus, using a shower gel formulation based on anionic and zwitterionic surfactants, the composition of which is given in table 11, the aim consisted in checking in this formulation the clearness, the viscosity and the suspension as influenced by various rheology modifying agents including reference products and those according to the invention.

(88) TABLE-US-00011 TABLE 11 1-DI water (double-deionized water) qsp 100 2-Texapon NSO UP (BASF) 32.14 3-Dehyton PK 45 (BASF) 6.67 4-Rheology modifying agent Polymer tested at 3% 5-Sodium hydroxide qs pH = 7.0 0.1 6-Potassium sorbate (Nutrinova) 0.40 7-Strawberry Fragrance (Hyteck) 0.50 8-Exfoson Quin 300 red, exfoliant particles 2.00 (Soniam)

(89) Protocol for Preparing the Formulation:

(90) The double-deionized water (1) is introduced in a beaker, and the various ingredients (2) and (3) are then added with stirring. After homogenization is complete, the rheology modifying agent (4) is added with very moderate stirring. The pH is measured, and is then adjusted to 7.00.1 with the ingredient (5). After checking the pH, the preserving agent (6) and the fragrance (7) are mixed with moderate stirring into the shower gel formulation. Finally, the quinoa exfoliant particles (8) are dispersed with stirring.

(91) Table 12 collates all of the rheology modifying agents that were used as ingredient (4) in the context of the tests of the present example 3.

(92) In table 12:

(93) REF: REFerence/INV: INVention/OINV: Outside INVention.

(94) TABLE-US-00012 TABLE 12 REF INV OINV NaCl Pol. 15 C3 Brookfield viscosity 6 rpm (mPa .Math. s) 17,800 17,100 9,100 Tan () 12 0.51 0.58 Elastic resistance (dyn/cm.sup.2) 0 115 40 T(500 nm) (%) 98 97 97