THERMO-STABILIZED AQUEOUS COMPOSITION

The invention relates to the preparation of an aqueous composition resistant to temperature variations thanks to the use of at least one particular heat-stabilizing agent (P). It also relates to the thermo-stabilization of the viscosity of the aqueous composition in a wide temperature range.

Many technical fields require the use of aqueous compositions. In particular, aqueous hydraulic binder compositions, aqueous adhesive compositions, aqueous detergent compositions, aqueous cosmetic compositions, aqueous ink compositions, aqueous paper coating compositions, aqueous coating compositions, in particular aqueous varnish compositions or aqueous paint compositions, in particular aqueous decorative paint compositions or aqueous industrial paint compositions.

In addition to their functional properties, these aqueous compositions must have a texture suitable for their use or for their storage. In particular, they must have a viscosity suitable for their use or their storage.

In addition, these aqueous compositions must be able to be used under conditions which can vary widely. In particular, these aqueous compositions must be used under variable temperature conditions. Indeed, the properties of these aqueous compositions can vary or deteriorate when the temperature varies, both for upward temperature variations and for downward temperature variations. In particular, the viscosity of these aqueous compositions can vary or deteriorate when the temperature varies. The functional properties of these aqueous compositions can therefore be altered in the event of variation or degradation of their viscosity during temperature variations.

There is therefore a need to be able to have aqueous compositions which do not have such disadvantages or aqueous compositions which do not lead to such problems.

In particular, it is particularly useful to be able to have aqueous coating compositions, in particular aqueous varnish compositions or aqueous paint compositions, the viscosity of which is thermally stable. Such aqueous compositions, the viscosity of which varies little or not at all, when the temperature at the time of their use is greater than 5° C. or when this temperature is less than 50° C., are particularly sought after. These properties are also sought for intermediate temperature ranges which correspond to frequently encountered conditions of use, for example from 5 to 15°C, from 15 to 35°C or from 30 to 50°C.

Furthermore, maintaining the viscosity and limiting the loss of viscosity of these aqueous compositions should be possible for wide shear rate ranges, for example from 0.1 to 1000 s 1 , from 0.1 to 100 s 1 , from 1 to 100 s 1 or from 0.1 to 1 s 1 .

Document EP 979833 describes thickening compounds for aqueous compositions to maintain or increase the viscosity of these compositions. These thickening compounds can be prepared from linear Cn-alkyl or linear Cn-alkyl itaconates or di-nonylphenol itaconates. Document WO 2011161508 describes (H)ASE polymers prepared using 2-acrylamido-2-methylpropane sulfonic acid and a monomer comprising a linear Cn-alkyl group. The article by Tarn et al. entitled Rheological properties of hydrophobically modified alkali-swellable polymers - effects of ethylene-oxide chain length, published in 1998, concerns a study of various effects of ethoxylated chain lengths in HASE polymers.

There is therefore a need for improved aqueous compositions.

The method according to the invention makes it possible to prepare an aqueous composition which provides a solution to all or part of the problems of the aqueous compositions of the state of the art. Thus, the invention provides a method for preparing an aqueous composition that is heat-resistant to temperature variations, comprising the addition of at least one heat-stabilizing agent (P) prepared by at least one polymerization reaction:

(al) at least one anionic monomer comprising at least one polymerizable olefinic unsaturation and at least one carboxylic acid function or one of its salts; (a2) at least one C 1 -C 7 ester of a compound derived from an acid chosen from acrylic acid, methacrylic acid, maleic acid and itaconic acid;

(a3) of at least one associative monomer of formula (I):

^-(OE OP R 2

(I)

in which :

- m and n, identical or different, independently represent 0 or an integer or decimal number less than 150, m or n is different from 0,

- OE independently represents a CH 2 CH 2 O group,

- OP independently represents a combination of CH 2 CH 2 O groups and groups chosen from CH(CH 3 )CH 2 0 and ϋ¾ϋί(ϋ¾)0,

- R 1 independently represents a group comprising at least one polymerizable olefinic unsaturation and

- R 2 independently represents a linear C 28 -C 40 -alkyl group or a branched C 28 -C 40 -alkyl group .

Preferably according to the invention, the aqueous composition is a composition chosen from a hydraulic binder composition, an adhesive composition, a detergent composition, a cosmetic composition, an ink composition, an aqueous paper coating composition, a of coating. Preferably according to the invention, the aqueous composition is a varnish composition or a paint composition or else a decorative paint composition or an industrial paint composition.

The aqueous composition according to the invention comprises at least one heat-stabilizing agent

(P).

Preferably according to the invention, the agent (P) is an associative compound. An associative compound makes it possible to produce associative bonds during the implementation of the composition according to the invention. These associative bonds generally develop between chemical groups of the same nature, in particular between hydrophobic groups. Preferably according to the invention, the monomer (al) is chosen from acrylic acid, methacrylic acid, a salt of acrylic acid, a salt of methacrylic acid and combinations thereof.

Also preferably according to the invention, the monomer (a2) is a C I -C 6 ester or a C 1 -C 4 ester or else is a C 1 -C 7 ester of acrylic acid or an ester C 1 -C 7 methacrylic acid, preferably chosen from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethylhexyl methacrylate and their combinations, more preferentially ethyl acrylate, butyl acrylate, methyl methacrylate and their combinations.

Also preferably according to the invention, the monomer (a3) ​​is a compound of formula (I) in which:

- m and n, identical or different, independently represent 0 or an integer or decimal number less than 150, m or n is different from 0,

- OE independently represents a CH 2 CH 2 O group,

- OP independently represents a combination of CH 2 CH 2 O groups and groups chosen from CH(CH 3 )CH 2 0 and CH 2 CH(CH 3 )0,

- R 1 independently represents a group comprising at least one polymerizable olefinic unsaturation and

- R 2 independently represents a linear C 32 -C 40 -alkyl group or a branched C 32 -C 40 -alkyl group or a linear C 30 -C 36 -alkyl group or a branched C 30 -C 36 -alkyl group ; preferably a linear C 32 -C 36 -alkyl group or a branched C 32 -C 36 -alkyl group ; more preferably a branched C 32 -alkyl group.

More preferably according to the invention, the monomer (a3) ​​is a compound of formula (I) in which:

- m and n, identical or different, independently represent 0 or an integer or decimal number less than 150, m or n is different from 0,

- OE independently represents a CH 2 CH 2 O group,

- OP independently represents a combination of CH 2 CH 2 O groups and groups chosen from CH(CH 3 )CH 2 0 and CH 2 CH(CH 3 )0,

- R 1 independently represents an acrylate group or a methacrylate group and

- R 2 independently represents a linear C 32 -C 40 -alkyl group or a branched C 32 -C 40 -alkyl group or a linear C 30 -C 36 -alkyl group or a branched C 30 -C 36 -alkyl group ; preferably a linear C 32 -C 36 -alkyl group or a branched C 32 -C 36 -alkyl group ; more preferably a branched C 32 -alkyl group.

Preferably according to the invention, the agent (P) is prepared by at least one polymerization reaction:

- from 20 to 55% by weight, of monomer (al),

- from 20 to 79.5% by weight, of monomer (a2),

- from 0.5 to 25% by weight, of monomer (a3),

relative to the total amount by weight of monomers.

Also preferably according to the invention, the agent (P) is prepared by at least one polymerization reaction:

- from 25 to 45% by weight, of monomer (al),

- from 35 to 74% by weight, of monomer (a2),

- from 1 to 20% by weight, of monomer (a3),

relative to the total amount by weight of monomers.

Also more preferably according to the invention, the agent (P) is prepared by at least one polymerization reaction:

- from 30 to 40% by weight, of monomer (al),

- from 45 to 67% by weight, of monomer (a2),

- from 3 to 15% by weight, of monomer (a3),

relative to the total amount by weight of monomers.

Also more preferably according to the invention, the agent (P) is prepared by at least one polymerization reaction:

- from 30 to 45% by weight, of monomer (al),

- from 43 to 65% by weight, of monomer (a2),

- from 5 to 12% by weight, of monomer (a3),

relative to the total amount by weight of monomers.

Agent (P) is generally known as such. It can be prepared by preparation methods of the state of the art. During the preparation of the agent (P) according to the invention, the quantities of reagents used can vary.

According to the invention, the heat-stabilizing agent (P) can be prepared by polymerization reaction of at least one compound (a1), at least one compound (a2) and at least one compound (a3) . The heat-stabilizing agent (P) can be prepared by polymerization reaction of the compounds (a1), (a2) and (a3) ​​alone.

In addition to the compounds (al), (a2) and (a3), the agent (P) can be prepared by a polymerization reaction also implementing:

(a4) at least one compound chosen from 2-acrylamido-2-methylpropane sulphonic acid, ethoxymethacrylate sulphonic acid, sodium methallyl sulphonate, styrene sulphonate phosphated hydroxyethyl-acrylate, phosphated hydroxypropyl-acrylate,

phosphated hydroxyethylhexyl-acrylate, phosphated hydroxyethyl-methacrylate, phosphated hydroxypropyl-methacrylate, phosphated hydroxyethylhexyl-methacrylate, their salts and their combinations, preferably less than 20% by weight or from 0.2 to 20% by weight, in particular of 0, 5 to 10% by weight of monomer (a4) relative to the total amount by weight of monomers or

(a5) at least one compound chosen from hydroxyethyl-acrylate, hydroxypropyl-acrylate, hydroxyethylhexyl-acrylate, hydroxyethyl-methacrylate, hydroxypropyl-methacrylate, hydroxyethylhexyl-methacrylate, preferably less than 20% by weight or from 0.2 to 20% by weight, in particular 0.5 to 10% by weight, of monomer (a5) relative to the total amount by weight of monomers or

(a6) at least one crosslinking monomer or at least one monomer comprising at least two olefinic unsaturations, preferably less than 5% by weight or from 0.01 to 4% by weight, in particular from 0.02 to 4% by weight or from 0.02 to 2% by weight or from 0.02 to 0.5% by weight, of monomer (a6) relative to the total quantity by weight of monomers or

(a7) at least one chain transfer agent, preferably at least one mercaptan compound, more preferably a mercaptan compound comprising at least four carbon atoms, even more preferably a mercaptan compound chosen from butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan , tert-dodecyl mercaptan and combinations thereof, preferably less than 5% by weight or 0.01 to 4% by weight, in particular 0.02 to 4% by weight or 0.02 to 2% by weight or 0.02 to 0.5% by weight of monomer (a7) relative to the total amount by weight of monomers.

The agent (P) can be implemented directly or else in a totally or partially neutralized form or even in a coacerbated form.

Preferably according to the invention, the agent (P) can be totally or partially neutralized, preferably by means of at least one compound chosen from NaOH, KOH, ammonium derivatives, ammonia, amino bases, for example triethanolamine, aminomethylpropanol or 2-amino-2-methyl-propanol (AMP) and combinations thereof.

Also preferably according to the invention, the agent (P) can be partially coacervated. Preferably, it can be coacerbated:

- by reducing the pH, for example by reducing the pH to a value below 6.5, in particular by means of an acid compound, in particular by means of at least one organic or mineral acid compound, in particular a chosen acid compound among phosphoric acid, citric acid, glucono-lactone, lactic acid, salicylic acid, glycolic acid, ascorbic acid, glutamic acid, hydrochloric acid, acetic acid, D-gluconic acid, sulfonic acid, methane-sulfonic acid, benzimidazole-sulfonic acid, tartaric acid, 4-aminobenzoic acid, benzoic acid, sorbic acid, phenylbenzimidazole sulfonic acid, benzylidene camphor sulfonic acid, terephthalylidene dicamphor sulfonic acid, kojic acid, hyaluronic acid or

- By increasing the ionic strength, for example by adding at least one ionized compound or at least one salt, in particular NaCl, KC1, MgCk, CaCk, MgSCk, CaS0 4 or by adding phenylbenzimidazole sulphonic acid (PBSA) or sodium salt of pyroglutamic acid (NaPCA).

According to the invention, the amounts of agent (P) used can vary. Preferably, the aqueous composition according to the invention comprises from 0.05 to 5% by weight, preferably from 0.1 to 2% by weight, of agent (P) relative to the total weight of the composition. According to the invention, the quantities of agent (P) used are expressed for the agent (P) as such, therefore dry.

The implementation of the heat-stabilizing agent (P) according to the invention provides a heat-resistant function or a function of resistance to temperature variations to the aqueous composition. These functions can be advantageously implemented when the aqueous composition is subjected to an increase in temperature or else when the aqueous composition is subjected to a decrease in temperature.

In addition to its action on the thermo-resistance or resistance to temperature variations of the aqueous composition according to the invention, the implementation of the agent (P) according to the invention makes it possible to influence the viscosity of the composition according to the invention. In particular, the agent (P) makes it possible to obtain an aqueous composition whose viscosity is thermo-stable at low shear gradient or at medium shear gradient, optionally at high shear gradient.

According to the invention, the effectiveness of the heat-stabilizing agent (P) is evaluated by measuring the viscosity and the change in this viscosity. Then, the agent (P) is implemented in an aqueous formulation for which the viscosity is evaluated after 24 hours by measuring flow curves for different shear gradients (Thermo Scientific Mars III rheometer using a cone-plane geometry of 60 mm in diameter and 1° angle) and at different temperatures. According to the invention, the initial viscosity is the viscosity measured at a particular shear rate before changing the temperature in a determined temperature range. The evolution of the viscosity can

then be evaluated by comparing a particular viscosity value with the initial viscosity.

Preferably, the evolution of the viscosity is evaluated for temperature variations ranging from 5 to 50°C or ranging from 30 to 50°C or ranging from 15 to 35°C or further ranging from 5 to 15°C. For these temperature ranges, the initial viscosity is the viscosity measured respectively at 5°C, at 30°C, at 15°C and at 5°C.

The effectiveness of the heat-stabilizing agent (P) according to the invention can be evaluated by comparison with analogous formulations which do not comprise heat-stabilizing agent (P) but a comparative polymer.

Essentially according to the invention, the heat-stabilizing agent (P) makes it possible to maintain the viscosity of the aqueous composition at high values ​​for wide temperature ranges. Also, the heat-stabilizing agent (P) makes it possible to maintain the viscosity of the aqueous composition at high values ​​for numerous shear gradient values, preferably for wide temperature ranges. Thus, preferably according to the invention, the aqueous composition has a viscosity measured for a shear rate ranging from 0.1 to 1000 s 1 and for a temperature variation ranging from 5 to 50° C., between 50% and 98%, preferably between 61% and 98%, of the initial viscosity value of the aqueous composition.

Also according to the invention, the aqueous composition has a viscosity measured for a shear gradient ranging from 0.1 to 1000 s 1 and for a temperature variation ranging from 30 to 50° C., between 70% and 98%, preferably between 79% and 98%, of the initial viscosity value of the aqueous composition.

Also according to the invention, the aqueous composition has a viscosity measured for a shear gradient ranging from 0.1 to 1000 s 1 and for a temperature variation ranging from 15 to 35° C., between 70% and 98%, preferably between 79% and 98%, the initial viscosity value of the aqueous composition.

Also according to the invention, the aqueous composition has a viscosity measured for a shear gradient ranging from 0.1 to 1000 s 1 and for a temperature variation ranging from 5 to 15° C., between 80% and 98%, preferably between 86% and 98%, of the initial viscosity value of the aqueous composition.

Also preferably according to the invention, the aqueous composition has a viscosity measured for a shear rate ranging from 0.1 to 100 s 1 and for a temperature variation ranging from 5 to 50° C., between 50% and 98 %, preferably between 58% and 98%, of the initial viscosity value of the aqueous composition.

Also according to the invention, the aqueous composition has a viscosity measured for a shear gradient ranging from 0.1 to 100 s 1 and for a temperature variation ranging from 30 to 50° C., between 70% and 98%, of preferably between 78% and 98%, of the initial viscosity value of the aqueous composition.

Also according to the invention, the aqueous composition has a viscosity, measured for a shear gradient ranging from 0.1 to 100 s 1 and for a temperature variation ranging from 15 to 35° C., between 70% and 98%, of preferably between 77% and 98%, of the initial viscosity value of the aqueous composition.

Also according to the invention, the aqueous composition has a viscosity, measured for a shear gradient ranging from 0.1 to 100 s 1 and for a temperature variation ranging from 5 to 15° C., between 80% and 98%, of preferably between 88% and 98%, of the initial viscosity value of the aqueous composition.

Also preferably according to the invention, the aqueous composition has a viscosity measured for a shear rate ranging from 1 to 100 s 1 and for a temperature variation ranging from 5 to 50° C., between 50% and 98%, preferably between 58% and 98%, of the initial viscosity value of the aqueous composition.

Also according to the invention, the aqueous composition has a viscosity measured for a shear gradient ranging from 1 to 100 s 1 and for a temperature variation ranging from 30 to 50° C., between 70% and 98%, preferably between 78% and 98%, of the initial viscosity value of the aqueous composition.

Also according to the invention, the aqueous composition has a viscosity measured for a shear rate ranging from 1 to 100 s 1 and for a temperature variation ranging from 15 to 35° C., between 70% and 98%, preferably between 78% and 98%, of the initial viscosity value of the aqueous composition.

Also according to the invention, the aqueous composition has a viscosity measured for a shear gradient ranging from 1 to 100 s 1 and for a temperature variation ranging from 5 to 15° C., between 80% and 98%, preferably between 88% and 98%, of the initial viscosity value of the aqueous composition.

Also preferably according to the invention, the aqueous composition has a viscosity measured for a shear rate ranging from 0.1 to 1 s 1 and for a temperature variation ranging from 5 to 50° C., between 55% and 98 %, preferably between 62% and 98%, of the initial viscosity value of the aqueous composition.

Also according to the invention, the aqueous composition has a viscosity measured for a shear gradient ranging from 0.1 to 1 s 1 and for a temperature variation ranging from 30 to 50° C., between 70% and 98%, of preferably between 78% and 98%, of the initial viscosity value of the aqueous composition.

Also according to the invention, the aqueous composition has a viscosity measured for a shear gradient ranging from 0.1 to 1 s 1 and for a temperature variation ranging from 15 to 35° C., between 70% and 98%, of preferably between 78% and 98%, of the initial viscosity value of the aqueous composition.

Also according to the invention, the aqueous composition has a viscosity measured for a shear gradient ranging from 0.1 to 1 s 1 and for a temperature variation ranging from 5 to 15° C., between 80% and 98%, of preferably between 88% and 98%, of the initial viscosity value of the aqueous composition.

In addition to maintaining the viscosity, the heat-stabilizing agent (P) also advantageously makes it possible to heat-stabilize the viscosity of the aqueous composition for numerous shear gradient values ​​and for wide temperature ranges with respect to the initial viscosity of the aqueous composition. Thus, the agent (P) makes it possible to limit the loss of viscosity of the aqueous composition subjected to a variation in temperature. The agent (P) implemented according to the invention makes it possible to limit the loss of viscosity for different values ​​of shear gradient applied to the aqueous composition, therefore for different conditions of use of this composition.

The thermo-stabilization method according to the invention is particularly advantageous during temperature variations at the time of preparation or else at the time of transport or storage, and even more so at the time of application or use of the composition. aqueous according to the invention. Preferably, the thermo-stabilization method according to the invention makes it possible to limit or even avoid the reduction in the viscosity of the aqueous composition according to the invention during temperature variations at the time of application or use. of the aqueous composition according to the invention. Preferably,

Thus, the invention provides a method for heat-stabilizing the viscosity of an aqueous composition comprising the addition to the aqueous composition of at least one agent (P) according to the invention.

In a particularly advantageous manner, the thermostabilization method according to the invention makes it possible to limit or even avoid the reduction in the viscosity of the aqueous composition according to the invention during temperature variations.

Preferably, the method for heat-stabilizing the viscosity of an aqueous composition comprises the addition of at least one heat-stabilizing agent (P) to the aqueous composition for which the reduction in viscosity measured for a gradient of shear ranging from 0.1 to 1000 s 1 is less than 45%, preferably less than 39%, for a temperature range ranging from 5 to 50° C., relative to the initial viscosity of the aqueous composition.

Also according to the invention, the method of heat-stabilizing the viscosity of an aqueous composition comprises the addition of at least one heat-stabilizing agent (P) in the aqueous composition for which the reduction in viscosity measured for a shear gradient ranging from 0.1 to 1000 s 1 is less than 30%, preferably less than 21%, for a temperature range ranging from 30 to 50° C., relative to the initial viscosity of the aqueous composition.

Also according to the invention, the method of heat-stabilizing the viscosity of an aqueous composition comprises the addition of at least one heat-stabilizing agent (P) in the aqueous composition for which the reduction in viscosity measured for a shear gradient ranging from 0.1 to 1000 s 1 is less than 30%, preferably less than 25%, for a temperature range ranging from 15 to 35° C., relative to the initial viscosity of the aqueous composition.

Also according to the invention, the method of heat-stabilizing the viscosity of an aqueous composition comprises the addition of at least one heat-stabilizing agent (P) in the aqueous composition for which the reduction in viscosity measured for a shear gradient ranging from 0.1 to 1000 s 1 is less than 20%, preferably less than 14%, for a temperature range ranging from 5 to 15° C., relative to the initial viscosity of the aqueous composition.

Also preferably, the method for heat-stabilizing the viscosity of an aqueous composition comprises the addition of at least one heat-stabilizing agent (P) to the aqueous composition for which the reduction in viscosity measured for a gradient shear strength ranging from 0.1 to 100 s 1 is less than 50%, preferably less than 42%, for a temperature range ranging from 5 to 50° C., relative to the initial viscosity of the aqueous composition.

Also according to the invention, the method of heat-stabilizing the viscosity of an aqueous composition comprises the addition of at least one heat-stabilizing agent (P) in the aqueous composition for which the reduction in viscosity measured for a shear gradient ranging from 0.1 to 100 s 1 is less than 30%, preferably less than 22%, for a temperature range ranging from 30 to 50° C., relative to the initial viscosity of the aqueous composition.

Also according to the invention, the method of heat-stabilizing the viscosity of an aqueous composition comprises the addition of at least one heat-stabilizing agent (P) in the aqueous composition for which the reduction in viscosity measured for a shear gradient ranging from 0.1 to 100 s 1 is less than 30%, preferably less than 22%, for a temperature range ranging from 15 to 35° C., relative to the initial viscosity of the aqueous composition.

Also according to the invention, the method of heat-stabilizing the viscosity of an aqueous composition comprises the addition of at least one heat-stabilizing agent (P) in the aqueous composition for which the reduction in viscosity measured for a shear gradient ranging from 0.1 to 100 s 1 is less than 20%, preferably less than 12%, for a temperature range ranging from 5 to 15° C., relative to the initial viscosity of the aqueous composition.

Also preferably, the method for heat-stabilizing the viscosity of an aqueous composition comprises the addition of at least one heat-stabilizing agent (P) to the aqueous composition for which the reduction in viscosity measured for a gradient shear strength ranging from 1 to 100 s 1 is less than 50%, preferably less than 42%, for a temperature range ranging from 5 to 50° C., relative to the initial viscosity of the aqueous composition.

Also according to the invention, the method of heat-stabilizing the viscosity of an aqueous composition comprises the addition of at least one heat-stabilizing agent (P) in the aqueous composition for which the reduction in viscosity measured for a shear gradient ranging from 1 to 100 s 1 is less than 30%, preferably less than 22%, for a temperature range ranging from 30 to 50° C., relative to the initial viscosity of the aqueous composition.

Also according to the invention, the method of heat-stabilizing the viscosity of an aqueous composition comprises the addition of at least one heat-stabilizing agent (P) in the aqueous composition for which the reduction in viscosity measured for a shear gradient ranging from 1 to 100 s 1 is less than 30%, preferably less than 22%, for a temperature range ranging from 15 to 35° C., relative to the initial viscosity of the aqueous composition.

Also according to the invention, the method of heat-stabilizing the viscosity of an aqueous composition comprises the addition of at least one heat-stabilizing agent (P) in the aqueous composition for which the reduction in viscosity measured for a shear gradient ranging from 1 to 100 s 1 is less than 20%, preferably less than 12%, for a temperature range ranging from 5 to 15° C., relative to the initial viscosity of the aqueous composition.

Also preferably, the method for heat-stabilizing the viscosity of an aqueous composition comprises the addition of at least one heat-stabilizing agent (P) to the aqueous composition for which the reduction in viscosity measured for a gradient shear strength ranging from 0.1 to 1 s 1 is less than 50%, preferably less than 38%, for a temperature range ranging from 5 to 50° C., relative to the initial viscosity of the aqueous composition.

Also according to the invention, the method of heat-stabilizing the viscosity of an aqueous composition comprises the addition of at least one heat-stabilizing agent (P) in the aqueous composition for which the reduction in viscosity measured for a shear gradient ranging from 0.1 to 1 s 1 is less than 30%, preferably less than 22%, for a temperature range ranging from 30 to 50° C., relative to the initial viscosity of the aqueous composition.

Also according to the invention, the method of heat-stabilizing the viscosity of an aqueous composition comprises the addition of at least one heat-stabilizing agent (P) in the aqueous composition for which the reduction in viscosity measured for a shear gradient ranging from 0.1 to 1 s 1 is less than 30%, preferably less than 22%, for a temperature range ranging from 15 to 35° C., relative to the initial viscosity of the aqueous composition.

Also according to the invention, the method of heat-stabilizing the viscosity of an aqueous composition comprises the addition of at least one heat-stabilizing agent (P) in the aqueous composition for which the reduction in viscosity measured for a shear gradient ranging from 0.1 to 1 s 1 is less than 20%, preferably less than 12%, for a temperature range ranging from 5 to 15° C., relative to the initial viscosity of the aqueous composition.

Preferably, for the thermo-stabilization method according to the invention, 0.05 to 5% by weight, preferably 0.1 to 2% by weight, of agent (P) is added to the aqueous composition per relative to the total weight of the composition.

The invention also provides a method for improving the resistance to temperature variations of an aqueous composition comprising the addition to the aqueous composition of at least one heat-stabilizing agent (P) defined according to the invention. In a particularly advantageous manner, the method for improving the resistance to temperature variations according to the invention makes it possible to limit or even avoid the reduction in the viscosity of the aqueous composition, preferably during temperature variations at the time of preparation. or else at the time of transport or storage or even at the time of application or use of the aqueous composition according to the invention.

Preferably according to the invention, the method for improving the resistance to temperature variations of an aqueous composition is implemented at a temperature ranging from 5 to 50° C. or ranging from 30 to 50° C. or ranging from 15 to 35°C or even ranging from 5 to 15°C.

Preferably, for the method for improving the resistance to temperature variations according to the invention, 0.05 to 5% by weight, preferably 0.1 to 2% by weight, is added to the aqueous composition. agent (P) relative to the total weight of the composition.

The aqueous composition according to the invention can be implemented in several technical fields. Preferably, the aqueous composition according to the invention is used in the field of materials, in particular in the form of a hydraulic binder composition or of an adhesive composition, in the field of detergents, in particular in the form of a detergent composition, in the field of cosmetics, in particular in the form of a cosmetic composition, in the field of printing, in particular in the form of an ink composition, in the field of papermaking, in particular in the form an aqueous composition for coating paper, in the field of coatings, for example in the fields of varnishes or paints, in particular in the form of a coating composition,

The invention therefore provides a formulation F comprising at least one aqueous composition according to the invention in combination with at least one functional substance useful in the field of use of the formulation.

Preferably, the formulation according to the invention is a coating composition, in particular a varnish composition or a paint composition. The formulation according to the invention then combines at least one aqueous composition according to the invention and at least one substance chosen from an organic or mineral pigment, organic particles, organo-metallic particles, mineral particles, for example calcium carbonate, talc, kaolin, mica, silicates, silica, metal oxides, in particular titanium dioxide, iron oxides. The formulation according to the invention may also comprise at least one agent chosen from a particle spacer, a dispersing agent, a steric stabilizing agent, an electrostatic stabilizing agent, an opacifying agent, a solvent, a coalescing agent, an anti -mousse,

Furthermore, the formulation according to the invention may be a concentrated aqueous pigment paste comprising at least one aqueous composition according to the invention and at least one organic or inorganic colored pigment.

The examples which follow make it possible to illustrate the various aspects of the invention.

EXAMPLES

Example 1: preparation of a compound (PI) according to the invention and of a comparative compound

In a 3 L glass reactor (receptacle 1) equipped with mechanical stirring, a vacuum pump, a nitrogen inlet and heated by means of a double jacket in which oil circulates, 890 g of bipermuted water are introduced and heated to 75° C. under an inert atmosphere. 10.5 g of powdered sodium dodecyl sulphate are then added and the medium is stirred until complete dissolution. In a 1000 mL glass beaker (receptacle 2) equipped with a magnetic stirrer, 338 g of bipermuted water, 3.4 g of powdered sodium dodecyl sulphate are successively added, which are stirred until dissolved. complete, 317 g of ethyl acrylate, 186.2 g of methacrylic acid and 19,1 represents a methacrylate group, m represents 25, OE represents an ethylene-oxy group, R 2 represents a branched C32-alkyl group). This mixture is stirred for 15 minutes to ensure good homogenization. Then, 1.83 g of ammonium persulphate and 0.183 g of sodium metabisulphite are quickly added to container 1. Then, the contents of container 2 are injected into container 1 using a peristaltic pump at 120 minutes. After reacting for 2 hours, the temperature is increased to 80° C. for 30 minutes. The appropriate amount of water is then added in order to adjust the dry extract to 30% by mass. An aqueous emulsion of the heat-stabilizing agent (PI) according to the invention is obtained.

Analogously, a comparative compound (PCI) is prepared. In a 3 L glass reactor (receptacle 1) equipped with mechanical stirring, a vacuum pump, a nitrogen inlet and heated by means of a double jacket in which oil circulates, 920 g of bipermuted water are introduced and heated to 75° C. under an inert atmosphere. 12.9 g of powdered sodium dodecyl sulphate are then added and the medium is stirred until complete dissolution.

In a 1000 mL glass beaker (receptacle 2) fitted with a magnetic stirrer, 321 g of bipermuted water, 4.5 g of sodium dodecyl sulphate are successively added, which are stirred until completely dissolved, 311 .5 g of ethyl acrylate, 180 g of methacrylic acid and 27.2 g of behenic alcohol methacrylate ethoxylated with 25 equivalents of ethylene oxide. This mixture is stirred for 15 minutes to ensure good homogenization. Then, 1.8 g of ammonium persulphate and 0.18 g of sodium metabisulphite are quickly added to container 1. Then, the contents of container 2 are injected into container 1 using a peristaltic pump in 120 minutes. After reacting for 2 hours, the temperature is increased to 80° C. for 30 minutes. An aqueous emulsion of comparative compound (PCI) is obtained.

Example 2: preparation and evaluation of aqueous formulations comprising a heat-stabilizing agent (PI) according to the invention or a comparative compound (PCI)

In a 500 mL glass beaker, 6.7 g of aqueous emulsion of heat-stabilizing agent (PI) of Example 1 are weighed. 393.3 g of bipermuted water are then added in order to obtain 400 g of aqueous solution of the heat-stabilizing agent (PI). This solution is placed under vigorous mechanical stirring. Then, its pH is adjusted to 8+/-1 by adding a 50% by weight aqueous sodium hydroxide solution. Stirring is maintained for 2 minutes and then the gel is placed at rest for 24 hours.

Similarly, a comparative formulation FC1 comprising a comparative compound (PCI) rather than the agent (PI) is prepared.

In a 500 mL glass beaker, 8 g of aqueous emulsion of comparative compound (PCI) of example 1 are weighed. 392 g of bipermutated water are then added in order to obtain 400 g of aqueous solution of compound ( ICP). This solution is placed under vigorous mechanical stirring. Then, its pH is adjusted to 8+/-1 by adding a 50% by weight aqueous sodium hydroxide solution. Stirring is maintained for 2 minutes and then the gel is placed at rest for 24 hours.

The amount of water in the FC1 formulation can be adjusted so that this formulation has a starting viscosity comparable to that of the F1 formulation.

The thickening efficiency of the formulations is evaluated after 24 hours by measuring flow curves at different shear gradients (Thermo Scientific Mars III rheometer using a cone-plane geometry 60 mm in diameter and 1° angle) and for different temperatures. The thermal stability of the formulation is then evaluated by calculating the evolution of the viscosity as a function of the evolution of the temperature for the various shear gradients applied. The change in viscosity is calculated in a standardized manner with respect to the viscosity measured at 4.9°C, for each value of viscosity measured, the ratio R is calculated (viscosity measured at a certain temperature / viscosity measured at 4.9 °C) corresponding to the residual viscosity of each formulation evaluated.

The results of the viscosity values ​​and the R ratios for the F1 formulation comprising the agent (PI) according to the invention are presented in Table 1.

The results of viscosity values ​​and R-ratios for the comparative formulation FC1 comprising the comparative polymer (PCI) are shown in Table 2.

For different shear gradient values, the evolution of the viscosity of the formulations comprising an agent (PI) according to the invention or a comparative polymer (PCI) is compared for different temperature ranges by calculating the loss of viscosity. Viscosity loss results are shown in Table 3.

For many temperature ranges, it is found that the heat-stabilizing agents according to the invention make it possible to limit the loss of viscosity much more significantly than the comparative polymer. This stabilization of the viscosity is possible for shear gradient values ​​corresponding to numerous conditions of use or application of aqueous compositions.

CLAIMS

1. Method for preparing an aqueous composition heat-resistant to temperature variations comprising the addition of at least one heat-stabilizing agent (P) prepared by at least one polymerization reaction:

(al) at least one anionic monomer comprising at least one polymerizable olefinic unsaturation and at least one carboxylic acid function or one of its salts;

(a2) at least one C1-C7 ester of a compound derived from an acid chosen from acrylic acid, methacrylic acid, maleic acid and itaconic acid;

(a3) of at least one associative monomer of formula (I):

^-(OE OP R 2

(I)

in which :

- m and n, identical or different, independently represent 0 or an integer or decimal number less than 150, m or n is different from 0,

- OE independently represents a CH2CH2O group,

- OP independently represents a combination of CH2CH2O groups and groups chosen from CH(CH 3 )CH 2 0 and ϋ¾OH(ϋ¾)0,

- R 1 independently represents a group comprising at least one polymerizable olefinic unsaturation and

- R 2 independently represents a linear C28-C40-alkyl group or a C28-C4o-alkyl group.

2. Method according to claim 1 for which the aqueous composition is a composition chosen from a hydraulic binder composition, an adhesive composition, a detergent composition, a cosmetic composition, an ink composition, an aqueous composition for coating paper, a coating composition, preferably a varnish composition or a paint composition or else a decorative paint composition or an industrial paint composition.

3. Method according to one of claims 1 and 2 for which:

* the monomer (al) is chosen from acrylic acid, methacrylic acid, a salt of acrylic acid, a salt of methacrylic acid and combinations thereof or

* the monomer (a2) is a C I -C 6 ester OR a C1-C4 ester or else is a C1-C7 ester of acrylic acid or a C1-C7 ester of methacrylic acid, preferably chosen from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethylhexyl methacrylate and combinations thereof, more preferably ethyl acrylate, butyl acrylate, methyl methacrylate and their combinations or

* the monomer (a3) ​​is a compound of formula (I) in which:

- m and n, identical or different, independently represent 0 or an integer or decimal number less than 150, m or n is different from 0,

- OE independently represents a CH2CH2O group,

- OP independently represents a combination of CH2CH2O groups and groups chosen from CH(CH 3 )CH 2 0 and CH 2 CH(CH 3 )0,

- R 1 independently represents an acrylate group or a methacrylate group and

- R 2 independently represents a linear C32-C40-alkyl group or a branched C32-C40-alkyl group or a linear C30-C36-alkyl group or a branched C30-C36-alkyl group; preferably a linear C32-C36-alkyl group or a branched C32-C36-alkyl group; more preferably a branched C32-alkyl group.

4. Method according to one of claims 1 to 3 for which the polymerization reaction implements:

- from 20 to 55% by weight, preferably from 25 to 45% by weight, more preferably from 30 to 40% by weight or from 30 to 45% by weight, of monomer (al),

- from 20 to 79.5% by weight, preferably from 35 to 74% by weight, more preferably from 45 to 67% by weight or from 43 to 65% by weight, of monomer (a2),

- from 0.5 to 25% by weight, preferably from 1 to 20% by weight, more preferably from 3 to 15% by weight or from 5 to 12% by weight, of monomer (a3)

relative to the total amount by weight of monomers.

5. Method according to one of claims 1 to 4 for which the agent (P) is prepared by a polymerization reaction also implementing:

(a4) at least one compound chosen from 2-acrylamido-2-methylpropane sulphonic acid, ethoxymethacrylate sulphonic acid, sodium methallyl sulphonate, styrene sulphonate phosphated hydroxyethyl-acrylate, phosphated hydroxypropyl-acrylate, phosphated hydroxyethylhexyl-acrylate, hydroxyethyl -phosphate methacrylate, phosphate hydroxypropyl methacrylate, phosphate hydroxyethylhexyl methacrylate, their salts and their combinations, preferably less than 20% by weight or from 0.2 to 20% by weight, in particular from 0.5 to 10% by weight , of monomer (a4) relative to the total amount by weight of monomers or

(a5) at least one compound chosen from hydroxyethyl-acrylate, hydroxypropyl-acrylate, hydroxyethylhexyl-acrylate, hydroxyethyl-methacrylate, hydroxypropyl-methacrylate, hydroxyethylhexyl-methacrylate, preferably less than 20% by weight or from 0.2 to 20% by weight, in particular 0.5 to 10% by weight, of monomer (a5) relative to the total amount by weight of monomers or

(a6) at least one crosslinking monomer or at least one monomer comprising at least two olefinic unsaturations, preferably less than 5% by weight or from 0.01 to 4% by weight, in particular from 0.02 to 4% by weight or from 0.02 to 2% by weight or from 0.02 to 0.5% by weight, of monomer (a6) relative to the total amount by weight of monomers or (a7) at least one chain transfer agent , preferably at least one mercaptan compound, more preferably a mercaptan compound comprising at least four carbon atoms, much more preferably a mercaptan compound chosen from butyl mercaptan, n-octylmercaptan, n-dodecylmercaptan, tert-dodecylmercaptan and combinations thereof, preferably less from 5% by weight or from 0.01 to 4% by weight, in particular from 0.02 to 4% by weight or from 0.02 to 2% by weight or from 0.02 to 0.5% by weight,of monomer (a7) relative to the total amount by weight of monomers.

6. Method according to one of claims 1 to 5 for which:

* the agent (P) is totally or partially neutralized, preferably by means of at least one compound chosen from NaOH, KOH, ammonium derivatives, ammonia, amino bases, for example triethanolamine, aminomethylpropanol or 2-amino-2-methyl -propanol (AMP) and combinations thereof or

* the agent (P) is partially coacervated, preferably:

- by reducing the pH, for example by reducing the pH to a value below 6.5, in particular by means of an acid compound, in particular by means of at least one organic or mineral acid compound, in particular a chosen acid compound among acid

phosphoric, citric acid, glucono-lactone, lactic acid, salicylic acid, glycolic acid, ascorbic acid, glutamic acid, hydrochloric acid, acetic acid, D-gluconic acid, sulfonic acid, methane-sulfonic acid, benzimidazole-sulfonic acid, tartaric acid , 4-aminobenzoic acid, benzoic acid, sorbic acid, phenylbenzimidazole sulfonic acid, benzylidene camphor sulfonic acid, terephthalylidene dicamphor sulfonic acid, kojic acid, hyaluronic acid or

- By increasing the ionic strength, for example by adding at least one ionized compound or at least one salt, in particular NaCl, KC1, MgCk, CaCk, MgSCk, CaS0 4 or by adding phenylbenzimidazole sulphonic acid (PBSA) or sodium salt of pyroglutamic acid (NaPCA).

7. Method according to one of claims 1 to 6 for which the aqueous composition comprises from 0.05 to 5% by weight, preferably from 0.1 to 2% by weight, of agent (P) relative to the weight composition total.

8. Method according to one of claims 1 to 7 for which the aqueous composition has:

- a viscosity measured for a shear rate ranging from 0.1 to 1,000 s 1 and for a temperature variation ranging from 5 to 50° C., between 50% and 98%, preferably between 61% and 98%, the initial viscosity value of the aqueous composition or

- a viscosity measured for a shear rate ranging from 0.1 to 100 s 1 and for a temperature variation ranging from 5 to 50° C., between 50% and 98%, preferably between 58% and 98%, of the initial viscosity value of the aqueous composition or

- a viscosity measured for a shear rate ranging from 1 to 100 s 1 and for a temperature variation ranging from 5 to 50° C., between 50% and 98%, preferably between 58% and 98%, of the value initial viscosity of the aqueous composition or

- a viscosity measured for a shear rate ranging from 0.1 to 1 s 1 and for a temperature variation ranging from 5 to 50° C., between 55% and 98%, preferably between 62% and 98%, of the initial viscosity value of the aqueous composition.

9. Method for heat-stabilizing the viscosity of an aqueous composition comprising the addition of at least one agent (P) defined according to one of claims 1 to 7 in the aqueous composition, for which:

- the decrease in viscosity measured for a shear rate ranging from 0.1 to 1000 s 1 is less than 45%, preferably less than 39%, for a temperature range ranging from 5 to 50°C, compared to the initial viscosity of the aqueous composition or

- the decrease in viscosity measured for a shear rate ranging from 0.1 to 100 s 1 is less than 50%, preferably less than 42%, for a temperature range ranging from 5 to 50° C., compared to the initial viscosity of the aqueous composition or

- the decrease in viscosity measured for a shear rate ranging from 1 to 100 s 1 is less than 50%, preferably less than 42%, for a temperature range ranging from 5 to 50°C, relative to the viscosity initial of the aqueous composition or

- the decrease in viscosity measured for a shear rate ranging from 0.1 to 1 s 1 is less than 50%, preferably less than 38%, for a temperature range ranging from 5 to 50° C., compared to the initial viscosity of the aqueous composition.

10. Thermostabilization method according to claim 9, for which 0.05 to 5% by weight, preferably 0.1 to 2% by weight, of agent (P) relative to the total weight of the composition.

11. Method for improving the resistance to temperature variations of an aqueous composition comprising the addition to the aqueous composition of at least one heat-stabilizing agent (P) defined according to one of claims 1 to 7.