THICKENING AGENT FOR A HYDRO-ALCOHOLIC COMPOSITION

Abstract

The invention relates to a thickening agent P for an aqueous composition, in particular for a hydro-alcoholic composition. The thickening agent P is prepared in the absence of acrylamide by a polymerisation reaction using N-methylol acrylamide or one of the derivatives thereof, an acid and an acid ester. A specific condensate of (meth)acrylic acid and N-methylol acrylamide are part of the invention. The invention also provides a hydro-alcoholic composition, the viscosity of the hydro-alcoholic composition being controlled.

The invention also provides a hydro-alcoholic composition, the viscosity of the hydro-alcoholic composition being controlled.

Claims

1. A thickening agent P prepared, in the absence of acrylamide, by at least one polymerisation reaction: of from more than 30% by weight to 69.75% by weight of at least one anionic monomer (a) chosen among acrylic acid, an acrylic acid salt, methacrylic acid, a methacrylic acid salt and combinations thereof; of from 29.75% by weight to less than 65% by weight of at least one non-ionic monomer (b) chosen among the C.sub.1-C.sub.8 esters of an acid chosen among acrylic acid, methacrylic acid and combinations thereof; of from 0.5 to 5% by weight of at least one compound (c) of formula I: ##STR00004## wherein: R.sup.1 independently represents H or CH.sub.3, R.sup.2 and R.sup.3, identical or different, independently represent H, CH.sub.3 or CH.sub.2CH.sub.3, relative to the total amount by weight of monomers (a), (b) and (c).

2. The agent P according to claim 1 for which compound (b) is chosen among methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, ethyl hexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethyl hexyl methacrylate, vinyl acetate and combinations thereof, more preferentially chosen among ethyl acrylate, butyl acrylate, methyl methacrylate and combination thereof.

3. The agent P according to one of claim 1, for which compound (c) is a compound of formula I wherein R.sup.2 and R.sup.3 represent H, preferably compound (c) is chosen among N-methylol-acrylamide, N-methylol-methacrylamide, more preferentially N-methylol-acrylamide.

4. The agent P according to one of claim 1, which is fully or partially neutralised, preferably by means of at least one compound chosen among NaOH, KOH, ammonium derivatives, ammonia, amine bases, for example triethanolamine or 2-amino-2-methyl-propanol (AMP) and combinations thereof, preferably by means of at least one compound chosen among the amine bases, for example triethanolamine or 2-amino-2-methyl-propanol (AMP).

5. The agent P according to one of claim 1, which is fully or partially coacervated, preferably which is fully or partially coacervated: by reducing the pH, for example by reducing the pH to a value of less than 6.5, in particular by means of an acid compound, in particular by means of least one organic or inorganic acid compound, in particular an acid compound chosen among phosphoric acid, citric acid, glucono-lactone, lactic acid, salicylic acid, glycolic acid, ascorbic acid, glutamic acid, hydrochloric acid, acetic acid, D-gluconic acid, sulphonic acid, methanesulphonic acid, benzimidazole sulphonic acid, tartaric acid, 4-aminobenzoic acid, benzoic acid, sorbic acid, phenylbenzimidazole sulphonic acid, benzylidene camphor sulphonic acid, terephthalylidene dicamphor sulphonic acid, kojic acid, hyaluronic acid or by increasing the ionic strength, for example by adding at least one ionised compound or at least one salt, in particular NaCl, KCl, MgCl.sub.2, CaCl.sub.2, MgSO.sub.4, CaSO.sub.4, or by adding phenylbenzimidazole sulphonic acid (PBSA) or pyroglutamic acid sodium salt (NaPCA) or even by adding at least one ionised organic sun filter.

6. The agent P according to one of claim 1, for which the polymerisation reaction uses: from 32.5 to 64.75% by weight of monomer (a), from 34.75 to 62.5% by weight of monomer (b) and from 0.5 to 5% by weight of monomer (c), relative to the total amount by weight of monomers (a), (b) and (c).

7. The agent P according to one of claim 1, for which the polymerisation reaction also uses at least one compound chosen among: d. a non-ionic (d) monomer chosen among C.sub.1-C.sub.8 esters of an acid chosen among itaconic acid, maleic acid, preferably a monomer (d) chosen among methyl itaconate, ethyl itaconate, propyl itaconate, butyl itaconate, methyl maleate, ethyl maleate, propyl maleate, butyl maleate and combinations thereof or e. a compound (e) of formula II: ##STR00005## wherein: T.sup.1 and T.sup.2, identical or different, independently represent H or CH.sub.3, Q.sup.1 and Q.sup.2, identical or different, independently represent H, CH.sub.3 or CH.sub.2CH.sub.3, preferably a compound (e) prepared by a prior reaction or by an in situ reaction between at least one compound (a) and at least one compound (c) of formula (I) defined according to one of the preceding claims, also preferably less than 8% by weight, preferably from 0.2 to 8% by weight, in particular from 0.5 to 5% by weight, of monomer (e) relative to the total amount by weight of monomers or f. at least one compound (0 chosen among 2-acrylamido-2-methylpropane sulphonic acid, ethoxymethacrylate sulphonic acid, sodium methallyl sulphonate, styrene sulphonate, hydroxyethyl acrylate phosphate, hydroxypropyl acrylate phosphate, hydroxyethylhexyl acrylate phosphate, hydroxyethyl methacrylate phosphate, hydroxypropyl methacrylate phosphate, hydroxyethylhexyl methacrylate phosphate, their salts and combinations thereof, preferably less than 20% by weight, preferably from 0.2% to 20% by weight, in particular from 0.5% to 10% by weight, of monomer (0 relative to the total amount by weight of monomers or g. at least one compound (g) chosen among hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethylhexyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethylhexyl methacrylate, preferably less than 20% by weight, preferably from 0.2 to 20% by weight, in particular from 0.5 to 10% by weight, of monomer (g) relative to the total amount by weight of monomers or h. a cross-linking monomer (h) or at least one monomer comprising at least two olefinic unsaturations, preferably less than 5% by weight, preferably from 0.01 to 4% by weight, in particular from 0.02 to 4% by weight or from 0.02 to 2% by weight, in particular from 0.02 to 1% by weight, of monomer (h) relative to the total amount by weight of monomers or i. at least one associative monomer (i), preferably chosen among a compound of formula (III):
G.sup.1-(OE).sub.m-(OP).sub.n-G.sup.2  (III) wherein: m and n, identical or different, independently represent 0 or an integer or decimal less than 150, m or n being different from 0, EO independently represents a CH.sub.2CH.sub.2O group, PO independently represents a group chosen among CH(CH.sub.3)CH.sub.2O and CH.sub.2CH(CH.sub.3)O, G.sup.1 represents a group comprising at least one polymerisable olefinic unsaturation, preferably an acrylate group or a methacrylate group and G.sup.2 represents a straight or branched C.sub.6-C.sub.40-alkyl group, a phenyl group, a polyphenyl group, preferably a straight or branched C.sub.10-C.sub.30-alkyl group, more preferentially a straight or branched C.sub.12-C.sub.22-alkyl group, or a group comprising 2 to 5 phenyls or a tristyrylphenyl group or a pentastyrylcumylphenyl group, preferably less than 20% by weight, preferably from 0.05 to 20% by weight, particularly from 0.1 to 10% by weight, of monomer (i) relative to the total quantity by weight of monomers.

8. The agent P according to one of claim 1, prepared from only compounds (a), (b) and (c).

9. The agent P according to one of claim 1 whose glass transition temperature is greater than −10° C. or greater than 0° C., preferably greater than 15° C. or greater than 25° C.

10. The agent P according to one of claim 1, which is a solid, preferably a powder.

11. The aqueous composition C comprising water and at least one agent P according to one of claim 1.

12. The composition C according to claim 11, chosen among a detergent composition, a sanitary composition, a disinfectant composition, a cosmetic composition, a coating composition, a paper coating colour composition, a textile printing composition, a textile coating composition.

13. The composition C according to one of claim 11 also comprising at least one additive chosen among an alcohol, an oxidising compound, an emollient compound, a surfactant compound and combinations thereof, preferably also comprising at least one alcohol and optionally at least one additive chosen among an oxidising compound, an emollient compound, a surfactant compound and combinations thereof, more preferentially a composition C comprising: from 0.1 to 5% by weight of at least one agent P, from 45 to 9.9% by weight of water, from 50 à 90% by weight of at least one alcohol.

14. The composition C according to according to one of claim 11, which has a Brookfield viscosity, measured at 25° C. and at 6 rpm, comprised between 800 and 20,000 mPa.Math.s, preferably comprised between 1,000 and 15,000 mPa.Math.s or comprised between 5,000 and 15,000 mPa.Math.s.

15. The composition C according to one of claim 11, that has: a pH greater than 6 or greater than 6.5 or a pH less than 13, preferably less than 12, more preferentially less than 11 or a pH ranging from 6 to 13 or from 6 to 12 or from 6 to 11, also more preferentially ranging from 6.5 to 13 or from 6.5 to 12 or from 6.5 to 11.

16. A method for controlling the viscosity of an aqueous composition comprising the addition of at least one agent P according to one of claim 1 to an aqueous composition.

17. A method for preparing a hydroalcoholic solution comprising mixing, in water, at least one agent P according to one of claim 1 and at least one alcohol and optionally at least one additive chosen among an oxidising compound, an emollient compound, a surfactant compound and combinations thereof.

18. A compound of formula (II): ##STR00006## wherein: T.sup.1 and T.sup.2, identical or different, independently represent H or CH.sub.3, Q.sup.1 and Q.sup.2, identical or different, independently represent H, CH.sub.3 or CH.sub.2CH.sub.3.

Description

Example 1: Preparation and Characterisation of Agents P According to the Invention

Preparation and Characterisation of Copolymer (P1) According to the Invention

[0068] In the reactor, place an initial load comprised of 460 g of deionised water and 2.3 g of sodium dodecyl sulphate.

[0069] In a first glass beaker and according to the proportions listed in Table 1, weigh 121.37 g of monomer (a), 196.55 g of monomer (b), 5.67 g of monomer (c) of formula I wherein R.sup.1, R.sup.2 and R.sup.3 represent H, 1.92 g of sodium dodecyl sulphate and 145 g of deionised water.

[0070] In a second glass beaker, weigh 0.270 g of ammonium persulphate and then dissolve it in 45 g of deionised water.

[0071] Heat the reactor content to 86° C.±2° C.

[0072] Inject the reagents from the 2 beakers into the polymerisation reactor in 2 hours and 30 minutes at a temperature of 86° C.±2° C.

[0073] Then, inject 0.106 g of ammonium persulphate dissolved in 20 g of deionised water into the reactor in 1 hour.

[0074] Then, bake for 1 hour before allowing the medium to cool and then filtering it.

[0075] A copolymer (P1) is obtained at 30.5% by weight of solids content, the composition of which is broken down in Table 1.

Preparation and Characterisation of Copolymer (P2) According to the Invention

[0076] In the reactor, place an initial load comprised of 445 g of deionised water and 2.3 g of sodium dodecyl sulphate.

[0077] In a first glass beaker and according to the proportions listed in Table 1, weigh 108.95 g of monomer (a), 184.12 g of monomer (b), 24.85 g of another monomer (b), 5.67 g of monomer (c) of formula I wherein R.sup.1, R.sup.2 and R.sup.3 represent H, 1.92 g of sodium dodecyl sulphate and 140 g of deionised water.

[0078] In a second glass beaker, weigh 0.270 g of ammonium persulphate and then dissolve it in 45 g of deionised water.

[0079] Heat the reactor content to 86° C.±2° C.

[0080] Inject the reagents from the 2 beakers into the polymerisation reactor in 2 hours and 30 minutes at a temperature of 86° C.±2° C.

[0081] Then, inject 0.106 g of ammonium persulphate dissolved in 20 g of deionised water into the reactor in 1 hour.

[0082] Then, bake for 1 hour before allowing the medium to cool and then filtering it.

[0083] A copolymer (P2) is obtained at 30.5% by weight of solids content, the composition of which is broken down in Table 1.

Preparation and Characterisation of Copolymer (P3) According to the Invention

[0084] In the reactor, place an initial load comprised of 460 g of deionised water and 2.3 g of sodium dodecyl sulphate.

[0085] In a first glass beaker and according to the proportions listed in Table 1, weigh 110.76 g of monomer (a), 185.95 g of monomer (b), 16.18 g of another monomer (b), 5.67 g of monomer (c) of formula I wherein R.sup.1, R.sup.2 and R.sup.3 represent H, 1.92 g of sodium dodecyl sulphate and 145 g of deionised water.

[0086] In a second glass beaker, weigh 0.270 g of ammonium persulphate and then dissolve it in 45 g of deionised water.

[0087] Heat the reactor content to 86° C.±2° C.

[0088] Inject the reagents from the 2 beakers into the polymerisation reactor in 2 hours and 30 minutes at a temperature of 86° C.±2° C.

[0089] Then, inject 0.106 g of ammonium persulphate dissolved in 20 g of deionised water into the reactor in 1 hour.

[0090] Then, bake for 1 hour before allowing the medium to cool and then filtering it.

[0091] A copolymer (P3) is obtained at 30.2% by weight of solids content, the composition of which is broken down in Table 1.

Preparation and Characterisation of Copolymer (P4) According to the Invention

[0092] In the reactor, place an initial load comprised of 450 g of deionised water and 2.97 g of sodium dodecyl sulphate.

[0093] In a first glass beaker and according to the proportions listed in Table 1, weigh 126.77 g of monomer (a), 158.25 g of monomer (b), 4.46 g of monomer (c) of formula I wherein R.sup.1, R.sup.2 and R.sup.3 represent H, 7.90 g of monomer (i) compound of formula III wherein G.sup.1 represents a methacrylate group, G.sup.2 represents a straight C.sub.22-alkyl group, m represents 25 and n represents 0 (C22-EO25 methacrylate), 1.76 g of sodium dodecyl sulphate and 130 g of deionised water.

[0094] Heat the reactor content to 86° C.±2° C.

[0095] In a second glass beaker, weigh 0.194 g of ammonium persulphate and then dissolve it in 40 g of deionised water.

[0096] Inject the reagents from the 2 beakers into the polymerisation reactor in 2 hours at a temperature of 86° C.±2° C.

[0097] Then, inject 0.106 g of ammonium persulphate dissolved in 20 g of deionised water into the reactor in 1 hour.

[0098] Then, bake for 30 minutes before allowing the medium to cool and then filtering it.

[0099] A copolymer (P4) is obtained at 30.4% by weight of solids content, the composition of which is broken down in Table 1.

Preparation and Characterisation of Copolymer (P5) According to the Invention

[0100] In the reactor, place an initial load comprised of 445 g of deionised water and 2.3 g of sodium dodecyl sulphate.

[0101] In a first glass beaker and according to the proportions listed in Table 1, weigh 106.43 g of monomer (a), 181.61 g of monomer (b), 24.85 g of another monomer (b), 5.67 g of monomer (c), 1.92 g of sodium dodecyl sulphate and 140 g of deionised water and 5.03 g of triallyl cyanurate.

[0102] In a second glass beaker, weigh 0.270 g of ammonium persulphate and then dissolve it in 50 g of deionised water.

[0103] Heat the reactor content to 86° C.±2° C.

[0104] Inject the reagents from the 2 beakers into the polymerisation reactor in 2 hours and 30 minutes at a temperature of 86° C.±2° C.

[0105] Then, inject 0.106 g of ammonium persulphate dissolved in 20 g of deionised water into the reactor in 1 hour.

[0106] Then, bake for 1 hour before allowing the medium to cool and then filtering it.

[0107] A copolymer (P5) is obtained at 30.7% by weight of solids content, the composition of which is broken down in Table 1.

Preparation and Characterisation of Copolymer (P6) According to the Invention

[0108] In the reactor, place an initial load comprised of 465 g of deionised water and 6.47 g of sodium dodecyl sulphate.

[0109] In a first glass container and according to the proportions listed in Table 1, weigh 108.14 g of monomer (a), 184.11 g of monomer (b), 2.89 g of monomer (c) of formula I wherein R.sup.1, R.sup.2 and R.sup.3 represent H, 2.82 g of sodium dodecyl sulphate and 124.4 g of deionised water.

[0110] In a second glass container, weigh 0.914 g of ammonium persulphate and then dissolve it in 10 g of deionised water.

[0111] In a third glass container, weigh 0.099 g of sodium metabisulphite and then dissolve it in 10 g of deionised water.

[0112] In a fourth container, such as a disposable syringe, weigh 5.31 g of monomer (f) 2-acrylamido-2-methylpropane sulphonic acid sodium salt at 50% by weight in water.

[0113] Heat the reactor content to 76° C.±2° C.

[0114] Inject the reagents from the 4 containers into the polymerisation reactor in 2 hours at a temperature of 86° C.±2° C.

[0115] Then, inject 0.3 g of ammonium persulphate dissolved in 20 g of deionised water into the reactor in 1 hour.

[0116] Then, bake for 1 hour before allowing the medium to cool and then filtering it.

[0117] A copolymer (P6) is obtained at 30.2% by weight of solids content, the composition of which is broken down in Table 1.

Preparation and Characterisation of Copolymer (P7) According to the Invention

[0118] In the reactor, place an initial load comprised of 474.69 g of deionised water and 2.96 g of sodium dodecyl sulphate.

[0119] In a first glass beaker and according to the proportions listed in Table 1, weigh 148.29 g of monomer (a), 159.95 g of monomer (b), 2.44 g of monomer (c) of formula I wherein R.sup.1, R.sup.2 and R.sup.3 represent H, 7.89 g of monomer (i) compound of formula III wherein G.sup.1 represents a methacrylate group, G.sup.2 represents a straight C22-alkyl group, m represents 25 and n represents 0 (C22-EO25 methacrylate), 1.76 g of sodium dodecyl sulphate and 151.62 g of deionised water.

[0120] Heat the reactor content to 86° C.±2° C.

[0121] In a second glass beaker, weigh 0.194 g of ammonium persulphate and then dissolve it in 22 g of deionised water.

[0122] Inject the reagents from the 2 beakers into the polymerisation reactor in 2 hours at a temperature of 86° C.±2° C.

[0123] Then, inject 0.20 g of ammonium persulphate dissolved in 20 g of deionised water into the reactor in 1 hour.

[0124] Then, bake for 30 minutes before allowing the medium to cool and then filtering it.

[0125] A copolymer (P7) is obtained at 31.3% by weight of solids content of which the composition is broken down in Table 1.

TABLE-US-00001 TABLE 1 Monomère (quantité - % en poids) Agent (a) (b) (c) (f) (h) (i) P1 37.51 (AMA) 60.74 (AE) 1.75 (NMA) P2 33.67 (AMA) 56.90 (AE) 1.75 (NMA)  .sup. 7.68 (Abu) P3 34.77 (AMA) 58.37 (AE) 1.78 (NMA)  .sup. 5.08 (Abu) P4 42.63 (AMA) .sup. 53.22 (AD) 1.50 (NMA) 2.65 P5 32.89 (AMA) 56.12 (AE) 1.75 (NMA) 1.55  .sup. 7.68 (Abu) P6 36.31 (AA) .sup.  61.82 (AE) 0.97 (NMA) 0.89 (AMPS) P7 46.55 (AMA) .sup. 50.21 (Abu) 0.76 (NMA) 2.48

Example 2: Preparation and Characterisation of Comparative Copolymers

Preparation and Characterisation of Comparative Copolymer (CP1)

[0126] The synthesis method is similar to the method for preparing agent P1. In a first glass container and according to the proportions listed in Table 2, weigh 112.98 g of monomer (a), 159.13 g of monomer (b), 0.695 g of monomer (h) diallyl phthalate, 1.92 g of sodium dodecyl sulphate and 140 g of deionised water.

[0127] In a second glass beaker, weigh 0.270 g of ammonium persulphate and then dissolve it in 50 g of deionised water.

[0128] Heat the reactor content to 86° C.±2° C.

[0129] Inject the reagents from the 2 beakers into the polymerisation reactor in 2 hours and 30 minutes at a temperature of 86° C.±2° C.

[0130] Then, inject 0.106 g of ammonium persulphate dissolved in 20 g of deionised water into the reactor in 1 hour.

[0131] Then, bake for 1 hour before allowing the medium to cool and then filtering it.

[0132] A copolymer (CP1) is obtained at 30.1% by weight of solids content of which the composition is broken down in Table 2.

Preparation and Characterisation of Comparative Copolymer (CP2)

[0133] The synthesis method is similar to the method for preparing agent P2. In a first glass beaker and according to the proportions listed in Table 2, weigh 123.65 g of monomer (a), 165.30 g of monomer (b), 11.50 g of monomer (i) compound of formula III wherein G.sup.1 represents a methacrylate group, G.sup.2 represents a straight C.sub.22-alkyl group, m represents 25 and n represents 0 (C22-EO25 methacrylate), 1.92 g of sodium dodecyl sulphate and 140 g of deionised water.

[0134] In a second glass beaker, weigh 0.270 g of ammonium persulphate and then dissolve it in 50 g of deionised water.

[0135] Heat the reactor content to 86° C.±2° C.

[0136] Inject the reagents from the 2 beakers into the polymerisation reactor in 2 hours and 30 minutes at a temperature of 86° C.±2° C.

[0137] Then, inject 0.106 g of ammonium persulphate dissolved in 20 g of deionised water into the reactor in 1 hour.

[0138] Then, bake for 1 hour before allowing the medium to cool and then filtering it.

[0139] A copolymer (CP2) is obtained at 30.0% by weight of solids content of which the composition is broken down in Table 2.

TABLE-US-00002 TABLE 2 Monomère (quantité - % en poids) Polymère (a) (b) (c) (e) (f) (h) (i) PC1 41.41 (AMA) 58.33 (AE) 0 0 0 0.25 0 PC2 41.15 (AMA) 55.02 (AE) 0 0 0 0 3.83

Example 3: Preparation and Characterisation of Hydroalcoholic Compositions According to the Invention and of Comparative Hydroalcoholic Compositions

[0140] From agents P1 to P5 and comparative copolymers CP1 and CP2, hydroalcoholic compositions C1 to C5 and CC1 and CC2 are prepared using the ingredients mixed in water in the amounts shown in Table 3.

TABLE-US-00003 TABLE 3 Phase A Eau désionisée Diluant 23.15 g Peroxyde d'hydrogène 3% Biocide 9.63 g Glycérol 98% Émollient 4.21 g Ethanol 96% Désinfectant 18.53 g Phase B Agent P1 à P5 ou Copolymères Épaississant 12.00 g PC1 et Phase C Triethanolamine 50% Neutralisant 4.06 g Phase D Ethanol 96% Désinfectant 128.42 g Quantité totale 200.00 g

[0141] In a 250 mL beaker equipped with a stirrer with a Rayneri blade of 40 mm in diameter, the ingredients from phase A are added until a homogeneous mixture is obtained.

[0142] While stirring, the thickening agent or copolymer of phase B is added, then the neutralising agent of phase C. The stirring speed is increased when the viscosity increases while keeping air from being incorporated. After adding all the neutralising agent, stirring is continued for 10 minutes.

[0143] The rest of the ethanol from phase D is then added and the stirring is continued for 10 minutes. Then, the composition is centrifuged to remove any air bubbles.

[0144] Then, the viscosity of hydroalcoholic compositions C1 to C5 and CC1 and CC2 is measured. The composition is placed in a thermostatically-controlled bath at 25° C. for 1 hour and the viscosity is measured using a Brookfield viscometer at 6 rpm. The results are shown in Table 4.

TABLE-US-00004 TABLE 4 Agent épaississant ou Viscosité Brookfield Composition copolymère (mPa .Math. s) C1 P1 7 380 C2 P2 7 620 C3 P3 7 460 C4 P4 5 320 C5 P5 5 270 CC1 PC1   570 CC2 PC2   160

[0145] The agent P according to the invention makes it possible to prepare hydroalcoholic compositions with a high viscosity essential for the use of these compositions. This viscosity control is obtained with an agent P that is prepared in the absence of acrylamide.

[0146] The comparative copolymers do not make it possible to achieve an acceptable viscosity for hydroalcoholic compositions.