EP3177703A1

EP3177703A1 - Use in detergent compositions of polymers obtained by low-concentration, inverse emulsion polymerization with a low content of neutralized monomers

Info

Publication number: EP3177703A1
Application number: EP15759892.1A
Authority: EP
Inventors: Frédéric BLONDEL; Lionel Champagnon
Original assignee: SPCM SA
Current assignee: SPCM SA
Priority date: 2014-08-06
Filing date: 2015-08-05
Publication date: 2017-06-14
Anticipated expiration: 2035-08-05
Also published as: US20170218308A1; FR3024736A1; MX2017001486A; ES2716416T3; CN107018667A; TR201903816T4; BR112017002282A2; US10407649B2; CN107018667B; EP3177703B1; FR3024736B1; WO2016020622A1

Abstract

The present invention relates to the use, for the manufacture of a detergent liquid aqueous composition for household or industrial use, of a branched or crosslinked polymer obtained by water-in-oil inverse emulsion polymerization of an aqueous solution of one or more monomers, at least one of the monomers used being an acrylic monomer and one or more of the monomers used being a monomer bearing at least one weak acid function, the mole percentage of monomers bearing at least one weak acid function relative to all the monomers used being at least 30%, characterized in that: i) the polymerization is carried out with a concentration of all the monomers in aqueous solution belonging to the range of from 1.3 mmol to 3.6 mmol per gram of aqueous solution, ii) during the polymerization, at most 20% of the acid functions present on the monomers having at least one acid function are in neutralized form; to the resulting detergent compositions for household or industrial use and to the uses thereof for textile fibre treatment or surface treatment in particular.

Description

USE IN DETERGENT POLYMER COMPOSITIONS OBTAINED BY REVERSE EMULSION POLYMERIZATION LOW CONCENTRATION WITH A LOW RATE OF NEUTRALIZED MONOMERS

The invention relates to the technical field of detergent compositions for household or industrial use adapted to the cleaning and washing of various surfaces and more specifically to the use in this field of synthetic acrylic polymers comprising at least one weak acid function, obtained under particular conditions by the inverse emulsion polymerization process from at least one monomer carrying a weak acid function, as well as the corresponding detergent compositions.

"Household or industrial detergent compositions" means compositions for the cleaning of various surfaces, in particular of textile fibers, of hard surfaces of any kind such as dishes, floors, windows, wood surfaces, metal or composite. Such compositions correspond, for example, to detergents for washing clothes manually or in a washing machine, products for cleaning dishes manually or for dishwashers, detergents for washing house interiors such as kitchen elements. , toilets, furniture, floors, windows, and other cleaning products for general use. The detergent compositions for household or industrial use do not include compositions intended for cleaning keratin materials (skin, hair, etc.) and therefore do not include cosmetic compositions, dermatological compositions, or pharmaceutical compositions with a cleaning component. In the remainder of the description, the "detergent compositions for household or industrial use" may simply be called "detergent compositions".

These detergent compositions were first developed in the form of powders, but this form has disadvantages when in use: slow dissolution in cold water, generation of dust, difficulty of dosage. This is why liquid versions of these compositions have been developed and can solve the problems raised. Liquid detergents have gained popularity and have gradually replaced powdered detergents around the world.

the term "liquid compositions" includes compositions in the form of solution, gel or dispersion.

However, these liquid detergent compositions have required complex work of adaptation and formulation. One of the challenges of this adaptation has been and still is the mastery of rheology. Thickeners or rheology modifiers are therefore widely used in these compositions to adapt their viscosity to the requirements of the consumer, who often feels that "thick is better", but also to suspend or stabilize active agents present in the composition.

Natural and synthetic polymers are used as thickeners. There may be mentioned, for example, hydroxyceiluloses, carboxymethyl celluloses, polysaccharides, polyacrylamides, acrylic polymers, polyvinylalcohols, polyurethanes, polyvinyl pyrrolidones, ethylene polyoxides, etc. A problem encountered in thickening detergent compositions is related to the presence of surfactants, which are necessary for their cleaning function, and which degrade the rheotogic behavior of the compositions thickened with polymer. This results in a loss of viscosity or a lack of stability over time of this viscosity.

Various documents describe liquid detergent compositions. EP 0 759 966 B1 of Johnson & Son, Inc. proposes associative polymers for thickening detergents for laundry containing large amounts of nonionic surfactant: 5 to 30% by weight. In this document, the polymers used such as Acusoi® 820 sold by Rohm and Haas Co are obtained by emulsion polymerization and are generally called latices.

U.S. Patent No. 6,274,539 to The Procter & Gamble Company discloses hand dishwashing compositions containing, for example, 20 to 40% by weight of anionic surfactant, 3 to 10% by weight of nonionic surfactant, and 0.2 to 2% of a thickening agent corresponding to an associative copolymer of ethyl acrylate, steareth-20, and (meth) acrylic acid. Acusoi® 820 is cited as an example of such a thickening polymer.

Another patent application of the same company, application US 2006/0281660, proposes to thicken optimally dishwashing detergent compositions with high molecular weight polycarboxylates, such as commercial products brand Carbopoi® from Noveon, or Flogel ® 700 from SNF Roerger. All of these polymers are obtained by the precipitation polymerization technique.

US Pat. No. 7,973,004 to Hercules Incorporated discloses the use of a thickening agent in the form of an associative polymer whose hydrophobic parts are more resistant in the presence of surfactant. Example 6, relating to a cleaning formulation for household use, uses, as an associative polymer, a modified polyacetal polyether, Aquaflow® XLS500, which is a polymer obtained by the precipitation polymerization technique.

Patent Application GB 2 346 891 proposes to thicken cleaning compositions for hard surface cleaning with hydrophobically modified polycarboxylates, such as the commercial products Polygel® W30 from 3V UK Ltd and Rheovis CRX and CR from Allied Colloids .

The most effective polymers currently in the detergent compositions are therefore either crosslinked polycarboxylates or homopolymers of acrylic acid obtained by precipitation polymerization, such as Carbopoi®, or so-called polymers. associative compounds having a hydrophilic major part and hydrophobic parts such as Acusol® 820 obtained by emulsion polymerization. Nevertheless, it has been found in use that these polymers are still sensitive to the presence of surfactants in the detergent compositions.

It should also be noted that the polymers obtained by inverse emulsion polymerization are not used to thicken detergent compositions and are rather considered by the professionals in the field of detergent compositions to be ineffective as a thickening agent in these compositions.

It appears that there is a real need to improve existing detergent compositions. The object of the invention is to provide detergent compositions having a rheological behavior for easy use and which are suitable for the incorporation of a wide range of surfactants, and having excellent resistance to surfactants. In this context, the Applicant has developed polymers obtained by inverse emulsion polymerization having improved thickening performance, making them compatible with their use in detergent compositions. It has also been found that these polymers have better resistance to surfactants conventionally used in detergent compositions.

The object of this invention is therefore to propose, for thickening liquid detergent compositions, the use of an acrylic polymer obtained by implementing particular conditions in an inverse emulsion polymerization process, said polymer thus having a good Thickening efficiency and being compatible with its use in detergent compositions. Moreover, such polymers are resistant to surfactants conventionally used in such detergent compositions.

The present invention relates to the use, for the manufacture of an aqueous liquid detergent composition for household use or industry !, a branched or cross-linked polymer composed of the repetition of one or more monomeric units, with at least one of the monomeric units which corresponds to a monomer comprising an acrylic group and at least 30 mol% of the monomeric units which are carriers at least one weak acid function optionally in neutralized form, said polymer being obtained:

by polymerization of an aqueous solution of one or more monomers in water-in-oil inverse emulsion, at least one of the monomers used being an acrylic monomer and one or more of the monomers used being a monomer carrying at least one weak acid function, the molar percentage of monomers carrying at least one weak acid function with respect to all the monomers used being at least 30%, the aqueous phase containing at least one monomer acting as a branching agent, so that the polymerization leads to a plugged or cross-linked polymer, characterized in that:

i) the polymerization is carried out with a concentration of all the monomers in aqueous solution belonging to the range of 1.3 mmo! at 3.6 mmol per gram of aqueous solution,

ii) during the polymerization, at most 20% of the acid functions present on the monomers having at least one acid function are in neutralized form;

the polymerization being optionally followed by one or more of the following steps:

a dilution or a concentration of the emulsion obtained,

an isolation to obtain the polymer in the form of a powder; at least partial neutralization of the free acid functions present in the polymer obtained.

Such a polymer defined by its process of obtaining is named in the following description "thickening polymer", "acrylic polymer" or "polymer plugged or crosslinked".

The subject of the invention is also the use of such a thickening polymer for thickening an aqueous detergent liquid composition. for household or industrial use. Preferably, to obtain the desired thickening effect, the thickening polymer comprises a percentage of neutralized acid functions of 30 to 100% with respect to all the acid functions present on the polymer, obtained by a step of at least partial neutralization of the acid functions present on the polymer made after the polymerization, but before or after the preparation of the composition.

The invention also relates to liquid aqueous detergent compositions for household or industrial use comprising at least one such thickening polymer, the polymerization being followed by a step of at least partial neutralization of the acid functions present carried out before or after the incorporation of the polymer into the composition ; and optionally one or more of the following steps, carried out before the incorporation of the polymer into the composition:

a dilution or a concentration of the emulsion obtained,

an insulation to obtain the polymer in the form of a powder. The use of these polymers which are more resistant to surfactants in the manufacture of detergent compositions makes it possible to reduce the drop in viscosity due to the presence of the surfactant (s) incorporated in the composition.

Such detergent compositions for household or industrial use will be in particular in the form of a solution, gel or dispersion, and in particular an aqueous solution, an aqueous gel or an aqueous dispersion. By composition (in particular aqueous solution, gel or dispersion) is meant a composition comprising a part of water, and in particular a part of water representing at least 10% by weight of the mass of the composition.

By way of examples, these compositions relate to compositions suitable and intended for cleaning textile fibers, such as washing liquors by hand or in a washing machine; suitable for cleaning hard surfaces of all kinds such as dishes (whether for manual or dishwasher cleaning), floors, window panes, wood, metal or composite surfaces, furniture, kitchen elements, toilets; and cleaning products for general use. The detergent compositions for household or industrial use according to the invention do not include the compositions intended for cleaning keratin materials (skin, hair, etc.) and therefore do not include the cosmetic compositions, the dermatological compositions or the pharmaceutical compositions. with cleaning component.

The invention also relates to the use of a composition according to the invention for cleaning textile fibers, in particular for washing clothes manually or in a washing machine, or for cleaning a hard surface such as dishes, furniture, floors, windows, wood or metals, especially for cleaning dishes manually or in dishwashers ...

Such use includes the application of the composition on the surface to be cleaned, optionally followed by rinsing with water.

Uses and compositions according to the invention preferably have one or other of the following characteristics, or any combination thereof, or all of the following characteristics when they are not mutually exclusive. the other: during the polymerization, at most 10%, preferably at most 5%, and preferably at most 2%, acid functions present on the monomers having at least one acid function are in neutralized form; according to a particular embodiment, all the acid functions present on the monomers are in free acid form, during the polymerization;

the polymerization is carried out with a concentration of all the monomers in aqueous solution belonging to the range of from 1.7 to 3.3 mmol per gram of aqueous solution; the polymer comprises a molar percentage of monomeric units carrying one or more weak acid function (s), with respect to all the monomeric units carrying an acid function, of at least 50%, preferably from minus 70%, very preferably at least 80%;

all the monomers used for the preparation of the polymer are monomers having at least one ethylenic unsaturation;

the monomeric unit (s) carrying at least one weak acid function, in free form, is (are) chosen from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid and fumaric acid, acrylic acid being preferred;

the polymer is a copolymer comprising at least one neutral mortomeric unit chosen from acrylamide, methacrylamide, Ν, Ν-dimethylacrylamide, N-vinylmethylacetamide, N-vinylformamide, vinyl acetate, diacetoneacrylamide, N-vinylformamide, isopropyl acrylamide, N- (2-hydroxy-1,1-bis (hydroxymethyl) ethyl] propenamide, (2-hydroxyethyl) acrylate, (2,3-dihydroxypropyl) acrylate, methyte methacrylate, (2-hydroxyethyl methacrylate), (2,3-dihydroxypropyl) methacrylate and vinylpyrrolidone, or all monomeric units carrying at least one acid function present in the polymer are monomeric units bearing one or more several weak acid function (s), in particular, the polymer present in the composition is an acrylic acid / acrylamide copolymer with 30 to 100% of the functions of acrylic acid in neutralized form, or the polymer is a copolymer comprising at least one unit monomeric carrier of one or more function (s) strong acid, preferably, the molar percentage of monomer units carriers of one or more strong acid function (s) with respect to all the monomeric units is less than 50%, and preferably less than 30%, for example, the monomer unit (s) carrier (s) ( s) one or more strong acid function (s), in free form, is (are) chosen from acryiamidoalkylsulfonic acid such as 2-acrylamido-2-methylpropanesulfonic acid, in particular, the polymer present in the composition is a 2-acrylamido-2-methylspropanesulphonic acid / acrylic acid or 2-acrylamido-2-methylpropanesulphonic acid / acrylic acid / acrylamide copolymer, with from 30 to 100% of the acid functions present on the polymer which are under neutralized form;

the branching agent is chosen from methylenebisacrylamide (MBA), ethylene glycol di-acrylate, polyethylene glycol dimethacrylate, diacrylamide, cyanomethylacrylate, vinylylethylethyl acrylate, vinyloxymethacrylate, triallylamine, formaldehyde, glyoxal, glycidytethers such as ethylene glycol diglycidyl ether, epoxies and mixtures thereof; preferably, the amount of branching agent is between 5 and 10,000 ppm by weight relative to the total weight of monomers, and preferably between 100 and 5000 ppm;

the polymerization reaction is conducted in the presence of a water-in-oil emulsifier;

the polymerization is conducted with a transfer agent, for example, selected from methanol, isopropyl alcohol, sodium hypophosphite, 2-mercaptoethanol, sodium methallysulfonate and mixtures thereof; preferably, the amount of transfer agent is between 0 and 5000 ppm by weight relative to the total mass of monomers, and preferably between 10 and 2500 ppm;

the branched or crosslinked polymer used in the composition has a viscosity at 0.16% by weight in water demineralized product with a pH adjusted to 7 +/- 0.1 with sodium hydroxide, measured at 25 ° C with a Brookfleld RVT type apparatus (rotational speed 20 rpm), in the range of 2,000 mPa.s at 100,000 mPa.s, especially at the range of 3,000 mPa.s to 50,000 mPa.s; the procedure for measuring the viscosity of the aqueous polymer solution at 0.16% by weight is preferably as follows: in a beaker of 400 ml, 250 g of deionized water are introduced, followed by mechanical stirring (tripnel 500 rpm), the desired amount of polymer is gradually added with stirring to obtain a solution containing 0.16% by weight of acrylic polymer, preferably the added polymer is in the form (inverse emulsion, dry powder, solution in water ...) under which it is used for the preparation of the detergent composition; the pH is then adjusted to 7 +/- 0.1 with sodium hydroxide; at this pH, 100% of the acid functions present on the polymer are neutralized; the solution is left stirring for 15 minutes and then for 5 minutes at rest; the viscosity is then measured using a RVT type Brookfieid viscometer (speed of rotation 20 rpm). The plugged or crosslinked polymer present in the composition thus makes it possible to thicken the composition to a certain viscosity, measured at 25 ° C. with a Brookfieid apparatus, belonging to the range from 10 mPa.s to 100,000 mPa.s, especially to range from 100 mPa.s to 50,000 mPa.s; in particular, the compositions according to the invention will have a viscosity in the range of 500 mPa.s to 30,000 mPa.s;

the composition comprises from 0.01% to 10% by weight of branched or crosslinked acrylic polymer, relative to the total weight of the composition, and preferably from 0.1 to 5% by weight of connected or crosslinked polymer; the composition comprises one or more surfactant (s), preferably chosen from anionic and nonionic cleaning agents;

the composition comprises from 0.1% to 50% by weight of surfactant (s), preferably chosen from anionic and nonionic cleaning surfactants, relative to the total mass of the composition, and preferably from 1% to 50% by weight of surfactant (s); % to 30% by weight of surfactant (s), preferably chosen from anionic and nonionic cleaning surfactants, in particular chosen from those defined in the description which follows;

the composition comprises at least one additive chosen from: detergency builders, also referred to as "builders", antifouling agents, anti-redeposition agents, bleaching agents, fluorescence agents, suds suppressing agents, enzymes, chelating agents, neutralizing agents and pH adjusting agents;

The composition comprises at least one cleaning surfactant and at least one detergency builder as defined in the description which follows and, preferably, at least one other additive chosen from: antifouling agents, anti-redeposition agents , bleaching agents, fluorescence agents, suds suppressing agents, enzymes, chelating agents, neutralizing agents and pH adjusting agents, in particular chosen from those defined in the description which follows.

The thickening polymers used in the context of the invention and their method of production will firstly be described.

The polymers used in the context of the invention are composed of the repetition of one or more monomeric units, with at least one of the monomeric units corresponding to a monomer comprising an acrylic group. In other words, they correspond to homopolymers obtained by polymerization of a monomer comprising an acrylic group or copolymers obtained by copolymerization of a monomer mixture, at least one of which comprises an acrylic group. For the sake of simplicity, in the following description, such polymers may simply be called acrylic polymers.

In order to effectively fulfill their role of thickener, the polymers used in the context of the invention are water-soluble or hydro-swelling. The monomers used for the preparation of these polymers and in particular the level of hydrophilic monomers will be selected so as to obtain such properties.

By water-soluble polymer is meant a polymer which, dissolved by stirring in water at a temperature of 25 ° C at a concentration of 50 g / l, gives a solution free of insoluble particles.

By hydro-swelling polymer is meant a polymer which, dissolved in water at a temperature of 25 ° C, swells and thickens the solution.

The polymers used in the context of the invention are connected or crosslinked. By branched polymers is meant, in a conventional manner, nonlinear polymers which have side chains. The branched polymers include, in particular, star-shaped and comb-shaped polymers. By crosslinked polymer is meant, in a conventional manner, a non-linear polymer which is in the form of a three-dimensional network insoluble in water, but swellable in water.

The crosslinking is obtained by using a branching agent during the polymerization which is integrated in the aqueous phase. Such a branching agent corresponds to a monomer comprising two or more ethylenic unsaturations and is, for example, chosen from methylenebisacrylamide (MBA). ), ethylene glycol di-acrylate, polyethylene glycol dimethacrylate, diacrylamide, cyanomethylacrylate, vinyloxyethylacrylate, vinyloxymethacrylate, thallylamine, formaldehyde, glyoxal, glycidyl ethers such as ethylene glycol diglycidyl ether, epoxies and mixtures thereof.

It should be noted that, in the context of the invention, the total monomer concentration given in connection with the polymerization process includes the monomers acting as branching agent.

In the context of the invention, the Applicant was interested in the use of corresponding acrylic polymers or obtained from a reverse polymer emulsion prepared by water-in-oil reverse emulsion polymerization with use of a high molar percentage. monomers carrying one or more weak acid function (s) with respect to all the monomers used, and in particular comprising at least 30 mol% of monomers carrying at least one weak acid function. With such a level of monomers carrying a weak acid function, the inventors have demonstrated that the properties of the polymer obtained were really dependent, on the one hand, on the neutralization rate of the acid functions of the monomers used during the polymerization and on the other hand, the total concentration of the monomers in the aqueous phase. In an original manner compared to the approaches proposed in the prior art which recommend carrying out the polymerization with a high degree of neutralization of the acid functions, the Applicant has, in the context of the invention, turned towards a process for the polymerization of inverse emulsion of polymers having a low degree of neutralization and, in particular, a degree of neutralization of the acid functions present of at most 20%.

In the context of the invention, the applicant proposes to use such a polymer, obtained by polymerization of an aqueous solution of monomers in water-in-oil inverse emulsion, in which the polymerization is carried out with a concentration of all the monomers belonging to in the range of 1.3 mmol to 3.6 mmol per gram of aqueous solution. In addition, the plaintiff has shown that such a range of concentrations, unlike the higher concentrations used in particular in the prior art, was compatible with obtaining polymer with a low neutralization rate weak acid functions present and overcomes stability problems found in the prior art.

In the context of the invention, the polymer used is obtained by implementing a process for preparing a polymer by polymerization of an aqueous solution of one or more monomers in water-in-oil inverse emulsion, in which one or more monomers used comprise at least one acid function, the molar percentage of monomers carrying at least one weak acid function with respect to all the monomers used being at least 30%, characterized in that:

i) the polymerization is carried out with a concentration of all the monomers in aqueous solution belonging to the range from 1.3 mmol to 3.6 mmol per gram of aqueous solution,

II) during the polymerization, at most 20% of the acid functions present on the monomers used having at least one acid function are in neutralized form.

In particular, during the polymerization, at most 10%, preferably at most 5%, and preferably at most 2%, acid functions present on the monomers used having at least one acid function are in neutralized form, which allows to obtain thickening properties even more advantageous. According to a particular embodiment, 100% of the acid functions present on the monomers used are in free acid form, during the polymerization.

In the context of (Invention, optimally, the polymerization is carried out with a total concentration of monomers present in the aqueous solution belonging to the range of from 1.7 to 3.3 mmol per gram of aqueous solution. the invention, the concentrations of monomers are given in relation to the mass total aqueous solution (also called aqueous phase), that is to say monomer mass included.

In particular, it is therefore possible to conduct the polymerization with the following combinations:

a concentration of all the monomers in aqueous solution belonging to the range from 1.3 mmol to 3.6 mmol per gram of aqueous solution, with at most 20%, advantageously at most 10%, preferably at most 5% , and preferably at most 2% or even 0% of the acid functions present on the monomers having at least one acid function which are in neutralized form,

a concentration of all the monomers in aqueous solution belonging to the range from 1.7 mmol to 3.3 mmol per gram of aqueous solution, with at most 20%, advantageously at most 10%, preferably at most 5% and preferably at most 2% or even 0% of the acid functions present on the monomers having at least one acid function which are in neutralized form.

The molar percentage of monomers bearing at least one weak acid function relative to all the monomers used is preferably at least 50%, preferably at least 70%, very preferably at least 80%. Such molar percentages may be used with any of the above-mentioned monomer concentration / neutralization concentration combinations.

In the context of the invention, the polymerization will preferably be carried out with monomers which all have at least one ethylenic unsaturation.

Preferably, the polymerization is carried out with a single monomer carrying at least one weak acid function whose molar percentage relative to all the monomers used is at least 30%, which in free form is chosen from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid and fumaric acid. The monomer carrying at least one weak acidic functional group is very preferably acrylic acid in free form or with a degree of neutralization according to the invention (it is also possible to use several monomers carrying at least one weak acidic function). , in particular chosen from those previously listed, whose total molar percentage relative to all the monomers used is at least 30%, preferably one of these monomers is acrylic acid in free form or with a neutralization according to the invention.

The polymerization can be carried out with at least one monomer carrying at least one strong acid function. In this case, the polymerization is preferably carried out with a concentration of monomers carrying at least one strong acid function relative to all the monomers used by less than 50%, and preferably less than 30%. The polymerization may, for example, be carried out with a monomer carrying at least one strong acidic function which in free form is chosen from acrylamidoalkylsulphonic acids, such as 2-acrylamido-2-methylpropanesulphonic acid (ATBS). In this case, the polymerization may, for example, be carried out with a combination of acrylic acid / ATBS or acrylic acid / ATBS / acrylamide, the monomers adde being in free form or with a degree of neutralization according to the invention.

In the context of the invention, it has been found that by selecting a concentration of monomers belonging to the range from 1.3 mmol to 3.6 mmoles per gram of aqueous solution to carry out the inverse emulsion polymerization reaction, it was possible to prepare inverse emulsions of polymers carrying acid function with a low degree of neutralization, or even no neutralization, which are stable, that is to say without the observation of a rapid phenomenon of precipitation. In addition, it has been shown that such a range of concentrations, unlike the higher concentrations used in particular in the prior art, associated with a low neutralization of acid functions present, allowed to obtain polymers providing a thickening efficiency, after an at least partial neutralization step, higher than the polymers of the prior art obtained by inverse emulsion polymerization. In addition, it has been demonstrated that these polymers are more resistant to surfactants used in detergent compositions and that their use in the manufacture of detergent compositions made it possible to reduce the drop in viscosity due to the presence of surfactant (s). Their thickening efficiency is very satisfactory, unlike polymers obtained by inverse emulsion polymerization implementing other monomer concentration conditions and / or neutralization of acid functions. In addition, it has been demonstrated that these polymers are more resistant to surfactants than the polymers obtained by precipitation polymerization or emulsion polymerization used in the prior art and that their use in the manufacture of detergent compositions was compatible with the use of a wide range of surfactants.

By "monomer carrying at least one acid function" is meant a monomer carrying one or more free or neutralized acid function (s) (that is to say salified by action of a base). The term "acid function", without further precision, therefore designates both the acid functions in free form and in neutralized form. When a monomer has more than one acid function, it is possible to have only a part of the acid functions in neutralized form. The present acid function (s) may be a weak acid or strong acid function. In general, a monomer used in the context of the invention will comprise only weak acid functions or strong acid functions, and most often monomers carrying a single acid function will be used. The same definitions and preferences apply to the monomeric units present on the polymer obtained. By way of example of a monomer carrying at least one free acid weak function in the free form, of the -COOH type, mention may be made of acrylic acid, methacrylic acid, itaconic acid and crotonic acid, which comprise all of them have only one weak acid function, and maleic acid and fumaric acid, which in turn have two weak acid functions.

By way of example of a monomer carrying a strong acid function in free form, mention may be made of monomers bearing a phosphonic acid or sulphonic acid function, such as acrylamidoalkylsulphonic acids such as 2-acrylamido-2-metrylpropane acid. sulfonic acid.

In their neutralized form, the acid functions are in anionic form with a counterion or base-dependent cation used for neutralization, for example of the Na ⁺ type when the sodium hydroxide is used or NH ₄ + when the ammonia is used. . Conventionally, the control of the number of acid functions in the neutralized form is ensured by the choice of the pH of the aqueous monomer solution which will be adjusted according to the pKa of the acid functions present.

The polymerization can involve a single type of monomer, then chosen from monomers carrying at least one weak acid function or different types of monomers, at least one of which carries at least one weak acid function, with a proportion of acid functions present on the monomers used, and thus on the copolymer obtained, in a neutralized form which is less than or equal to 20%. In particular, in addition to the monomeric unit or units carrying at least one weak acid function previously described, the polymer obtained may contain other monomeric units such as monomeric units carrying at least one strong acid function, monomeric units. neutral (or nonionic) monomeric monomeric units and / or monomeric units with hydrophobic character. Whatever the case, the training conditions of the The aqueous and polymerization phases are such that the acid functions of the monomers used remain predominantly in free form, and are not neutralized by formation of a salified form, or weakly neutralized with a limited neutralization rate of less than or equal to 20%. . When a neutralization of less than or equal to 20% takes place, it is generally carried out in the aqueous phase, by adding an appropriate amount of base. A base such as sodium hydroxide or ammonia may be used.

In particular, the polymerization reaction can be carried out with at least one neutral monomer chosen from acrylamide, methacrylamide, Ν, Ν-dimethylacrylamide, N-vinylmethylacetamide, N-vinylformamide, vinyl acetate and diacetoneacrylamide. N-isopropyl acrylamide, N- [2-hydroxy-1,1-bls (hydroxymethyl) ethyllpropenamide, (2-hydroxyethyl) acrylate, (2,3-dihydroxypropyl) acrylate, methyl methacrylate , (2-hydroxyethyl) methacrylate, (2,3-dihydroxypropyl) methacrylate, vinylpyrrolidone, or other acrylic esters, or other ethylenically unsaturated esters. For example, the polymerization can be carried out with from 30 to 99 mol% of at least one monomer having one or more weak acid function (s) and from 1 to 70 mol% of at least one neutral monomer. The polymerization may, for example, be carried out with a combination of acrylic acid / acrylamide, the acrylic acid being in neutral form or with a degree of neutralization according to the invention.

It is also possible to carry out a copolymerization with at least one canonical monomer. As examples of canonical monomers, mention may be made of diallyldialkyl ammonium salts such as diallyl dimethyl ammonium chloride (DADMAC); acidified or quaternized salts of dialkylaminoalkyl acrylates and methacrylates, in particular dialkylaminoethyl acrylate (ADAME) and dialkylaminoethyl methacrylate (MADAME); acidified or quaternized salts of alkylaminoalkylamrylamides or methacrylamides, such as, for example methacrylamido-propyl trimethyl ammonium chloride (MAPTAC), acrylamido-propyl trimethyl ammonium chloride (APTAC) and Mannkrh products such as quaternized dialkylaminomethylacrylamides.

The acidified salts are obtained by the means known to those skilled in the art, and in particular by protonation. The quaternized salts are also obtained by means known to those skilled in the art, in particular by reaction with benzyl chloride, methyl chloride (MeCl), aryl chlorides, alkyl, or dimethylsulfate.

It is also possible to carry out a copolymerization with at least one hydrophobic monomer. Examples of hydrophobic monomers that may be mentioned include undecanoic acid acrylamide, undodecyl methyl acrylamide acid, acrylic acid derivatives such as alkyl acrylates or methacrylates, for example ethoxylated behenyl methacrylate. In this case, the molar percentage of hydrophobic monomers with respect to all the monomers used is preferably less than 10%, and generally between 0.001% and 7%. Copolymers obtained with such hydrophobic monomers give associative copolymers.

According to a first variant of the process according to the invention, all the monomers carrying at least one acid function used to carry out the polymerization are monomers carrying at least one weak acid function.

According to a second variant of the process according to the invention, the polymerization is carried out with at least one monomer carrying at least one strong acid function, in addition to at least one monomer carrying at least one weak acid function. In this case, the molar percentage of monomers carrying at least one strong acid function relative to all the monomers used is preferably less than 50%, very preferably less than 30%.

The copolymers obtained according to the method of the invention may in particular be formed from a combination of at least one unit monomeric carrier carrying at least one weak acid function and at least one monomeric unit carrying at least one strong acid function, and in particular corresponding to an acrylic acid / ATBS copolymer, these acid monomers being in neutral form or with a neutralization according to the invention; a combination of at least one monomeric unit carrying at least one weak acidic function with at least one neutral monomeric unit and optionally at least one monomeric unit carrying at least one strong acid function, and in particular corresponding to a copolymer acrylic acid / acrylamide or an acrylonic acid / ATBS / acrylamide copolymer, the acrylic acid and the ATBS being in neutral form or with a degree of neutralization according to the invention; a combination of at least one monomeric unit carrying at least one weak acid function with at least one cationic monomeric unit and optionally at least one monomeric unit carrying at least one strong acid function; or a combination of at least one monomeric unit carrying at least one weak acid function with at least one neutral monomeric unit and at least one cationic monomer and optionally at least one monomeric unit carrying at least one acidic function strong.

In the inverse emulsion polymerization process used in the context of the invention, the monomers are placed in aqueous solution. This aqueous solution corresponds to the aqueous phase of the inverse emulsion. In the context of the invention, in the aqueous solution used for the polymerization, at most 20% of the acid functions present on the monomers having at least one acid function are in neutralized form.

It is possible to use a transfer agent, otherwise known agent ^the chain imitator. The use of a transfer agent is particularly advantageous for controlling the molecular weight of the polymer obtained. By way of example, transfer agent may be methanol, isopropanol, sodium hypophosphite, 2- mercaptoethanol, sodium methallysulfonate and mixtures thereof. Those skilled in the art will adjust, in known manner, the used amounts of branching agent and optionally transfer agent, depending on whether it wishes to obtain a plugged or crosslinked polymer and the desired viscosity.

In more detail, the method used in the context of the invention comprises the following steps:

a) having an aqueous solution of the selected monomer or monomers, called the aqueous phase,

b) emulsifying said aqueous solution in a phase immiscible with water, called oil phase,

c) conducting the polymerization reaction.

Of course, the aqueous solution of step a) has a total concentration of monomers, a molar percentage of monomers carrying at least one weak acid function with respect to all the monomers used and a neutralization rate of the acid functions. present on the monomers having at least one acid function in accordance with the process described in the context of the invention.

In a conventional manner, step b) of emulsification of the aqueous phase in the oil phase will preferably be carried out by adding the aqueous phase to the oil phase kept under stirring.

In general, the polymerization reaction is carried out in the presence of a water-in-oil emulsifier. The latter is most often introduced into the oil phase in which the aqueous solution is emulsified. By emulsifying agent of the water-in-oil (W / O) type is meant a emulsifying agent having a sufficiently low HLB value to provide water-in-oil emulsions, and in particular an HLB value of less than 10.

The value of HLB is calculated according to the following relation:

HLB = (% by weight of the hydrophilic part) / 5 The weight percentage of the hydrophilic portion is the ratio of the molecular weight of the hydrophilic moiety to the total molecular weight of the molecule.

By way of examples of such water-in-oil emulsifying agents, there may be mentioned surfactant polymers such as polyesters with a molecular weight between 1000 and 3000 g / mol, the condensation products between a poly (isobutenyl) succinic acid or its anhydride. and a polyethylene glycol, block copolymers of molecular weight between 2500 and 3500 g / mol _f for example those sold under the names HYPERMER®, extracts of sorbitan, such as sorbitan monooleate, sorbitan or Pisostéarate ie sesquioiéate sorbitan certain polyethoxy-sorbitan esters, such as pentaethoxylated sorbitan monooleate or pentaethoxylated sorbitan isostearate, or diethoxylated oleocetyl alcohol, tetraethoxylated lauryl acrylate.

In the inverse emulsion polymerization process, the aqueous solution contains the monomer (s) and optionally the branching agent and the transfer agent. It may also contain compiexing agents such as ethylene diamine or ethylene diamine tetraacetic acid.

Most often, the polymerization reaction of step c) is initiated by introduction into the emulsion formed in step b) of a free radical initiator. By way of example of a free-radical initiator agent, mention may be made of the oxidizing-reducing pairs with, among the oxidants, cumene hydroperoxide or tertiary butylhydroxyperoxide, and among the reducing agents, persulfates such as sodium metabisulphite and salt. from Mohr. Alcohols such as 2,2'-azobis (isobutyronitrile) and 2,2'-azobis (2-aminopropane) hydrochloride can also be used.

In a conventional manner, the polymerization is generally carried out isothermally, adiabatically or at a controlled temperature. That is, the constant temperature is generally maintained between 10 and 50 ° C (isothermal), or the temperature is allowed to increase naturally (adiabatic) and in this case the reaction is generally started at a temperature below 10 ° C and the final temperature is generally above 50 ° C, or finally The rise in temperature is controlled to obtain a temperature curve between that of the isotherm and that of adiabatic.

It is possible to introduce at the end of the polymerization reaction one or more oil-in-water emulsifiers, preferably at a temperature below 50 ° C.

By emulsifying agent of the oil-in-water (O / W) type is meant an emulsifying agent having a sufficiently high HLB value to provide oil-in-water emulsions and in particular an HLB value of greater than 10. As examples of such oil-in-water emulsifiers, mention may be made of ethoxylated sorbitan esters such as sorbitan oleate ethoxylated with 20 equivalents of ethylene oxide (EO 20), sorbitan laurate polyethoxylated with 20 moles of ethylene oxide, polyethoxylated castor oil with 40 moles of ethylene oxide, decaethoxylated oierodecyl alcohol, heptaethoxylated lauric alcohol, or polyethoxylated sorbitan monostearate with 20 moles of ethylene oxide.

The quantities of emulsifying agent (s) introduced are such that the inverse emulsion of the polymer obtained will generally contain from 1% to 10% by weight, and preferably from 2.5% to 9% by weight, emulsifiers of the water-in-oil type (ξ / Η) and, optionally, from 2% to 10% by weight, and preferably from 2.5% to 6% by weight of oil-in-water emulsifiers (H / E).

In general, the mass ratio of the aqueous phase to the oil phase is 50/50 to 90/10.

The oil phase used in the inverse emulsion polymerization process may be composed, for example, of a mineral oil, in particular a commercial oil, containing saturated hydrocarbons of paraffinic, isoparaffinic, cycloparaffinic and naphthalic type exhibiting room temperature (22 ° C), a density between 0.7 and 0.9; a vegetable oil; a synthetic oil such as hydrogenated potydecene or hydrogenated polylsobutene; an ester such as octyl stearate or buthy! oleate; a vegetable oil such as squalane of vegetable origin; or a mixture of several of these oils.

At the end of the polymerization reaction, it is also possible that the emulsion obtained is diluted or concentrated. In particular, it is possible to concentrate the emulsion obtained by distillation or to completely dry it in order to obtain a powder. Such concentration or drying will be carried out with or without prior introduction of oil-in-water (O / W) emulsifier.

The inverse emulsions thus obtained can be concentrated, for example by distillation. Inverse emulsions are obtained, the polymer concentration of which can be between 30 and 75% by weight, preferably between 40 and 65% by weight.

The polymers obtained from the inverse emulsions subsequently subjected to an Isolation stage may be in the form of a powder. Such an isolation step may, for example, be selected from the techniques of precipitation, azeotropic distillation and spray drying.

Indeed, in the context of the invention, it is possible to concentrate or isolate the polymer in the form of an inverse emulsion obtained directly at the outlet of the inverse emulsion polymerization process, without losing the advantageous properties of the polymers obtained. . In particular, there are numerous processes for obtaining powder from inverse emulsions of polymers which consist in isolating the active ingredient from the other constituents of the emulsion, for example

precipitation in a non-solvent medium such as acetone, methanol or any other polar solvent in which the polymer is not soluble. A simple filtration then makes it possible to isolate the polymer particle. the azeotropic distillation in the presence of an agglomerating agent and of a stabilizing polymer makes it possible to lead to agglomerates which are easily isolated by filtration before drying the particle.

spray-drying or spray drying consists in creating a cloud of fine droplets of emulsions in a stream of hot air for a controlled period of time.

The polymers obtained after such steps retain their advantageous properties, in terms of thickening capacity and in terms of resistance to surfactants.

Without additional neutralization step, in the polymers obtained at the end of the inverse emulsion polymerization process or after a drying or concentration step, at most 20% of the acid functions present are in neutralized form, preferably at most 10% , even more preferably at most 5%, and preferably at most 2%. This low level of neutralization of the acid functions present gives the formulator great flexibility, allowing him to adjust the properties of the polymer and thus the desired thickening effect, by adjusting the neutralization rate. Such an approach also allows the formulator to choose the nature of the neutralizing agent used, compatible with the targeted use.

To obtain the desired thickening effect, the polymerization is most often followed by a neutralization step, otherwise called a post-neutralization step, of at least a part, or even all, of the free acid functions present on the polymer. . In the case where a step of at least partial neutralization of the free acid functions present in the polymer obtained is carried out after the polymerization reaction, it leads, preferably, to a percentage of neutralization with respect to all the acid functions present on the polymer from 30 to 100%.

Such a post-neutralization step can be carried out in different ways: the post-neutralization can be done on the inverse emulsion obtained at the end of the inverse emulsion polymerization process. Generally this is the case, when the manufacturer himself neutralizes the polymer in the form of an inverse emulsion, the post-neutralization can be done on an aqueous solution obtained following the inversion of the inverse emulsion in water. Generally, this is the case when the processor uses the reverse emulsion, or the powder resulting therefrom, in an aqueous solution, called the stock solution, before adding the latter to the composition to be thickened. He is then free to adjust the polymer concentration of the solution, the degree of neutralization and the nature of the neutralizing agents.

The post-neutralization can also be carried out on the composition in which the inverse emulsion or the powder resulting therefrom has been incorporated. In the same way as the previous case, the user has the freedom to adjust the neutralization rate and the nature of the neutralizing agents.

The neutralization is carried out using a base, similar to the monomer neutralization previously described in the context of the polymerization process, the nature and amounts of which are selected by those skilled in the art.

These polymers, thus neutralized, offer much better thickening properties and resistance to surfactants, all other conditions being equal, compared to polymers obtained by inverse emulsion polymerization which do not satisfy the concentration and neutralization conditions of the monomers as defined in the process according to the invention. the invention. Particularly after neutralization, the polymers offer advantageous properties over polymers consisting of the same monomers but prepared by inverse emulsion polymerization directly at higher neutralization rates and / or at a different total monomer concentration. Advantageously, the polymers used in the context of the invention allow after complete neutralization of the free acid functions present, or at least greater neutralization, to thicken much more effectively aqueous media present in detergent compositions.

The detergent compositions according to the invention and their method of preparation, and in particular the incorporation of the previously described polymers, will now be detailed.

the manufacture of detergent compositions is widely known to those skilled in the art. It generally consists of successively adding one or more cleaning surfactants and other ingredients such as additives in an aqueous solution.

The addition of the acrylic thickening polymer described above can be done at any stage of the manufacture of the detergent composition. The detergent composition preferably comprises from 0.01% to 10% by weight of thickening acrylic polymer described above, and preferably from 0.1 to 5% by weight, these percentages being given relative to the total mass of the composition.

The neutralization step leading to a percentage of acid functions neutralized from 30 to 100% with respect to all of the acid functions present on the polymer can be done before or after the incorporation of the polymer in the composition.

Furthermore, the advantageous properties of the polymer obtained by inverse emulsion polymerization according to the method described above retain its advantageous properties, whether it is in the form of a more or less concentrated inverse emulsion, a powder or a aqueous solution. Therefore, the thickening polymer according to the invention can be introduced into the detergent composition, in the form of an inverse emulsion, a powder or in solubilized form, for example in water or an organic solvent, or else in aqueous or organic dispersion form. Generally it is a form solubilized polymer in water which is introduced into the composition, obtained either by inversion of an inverse emulsion in water, is released by dissolution of a powder in water. Whatever the form in which it is introduced, in the detergent composition at the time of its use, the polymer will be in a solution, or aqueous phase in the case of a multi-phasic composition, in which it plays its role of thickener and stabilizer.

The composition according to the invention comprises an aqueous part composed of water and hydrophilic compounds, the composition may be in the form of a single aqueous portion (solution or gel) constituting the entire composition or a dispersion aqueous composition comprising solid particles such as mineral microparticles improving the cleaning properties. In the following description, we will name aqueous phase, the part of the composition comprising water and the hydrophilic components of the composition, and in particular the solubie components or miscible with water, even in the case of single-phase compositions, or composed exclusively of such an aqueous phase, the composition may comprise, in addition to water, at least one hydrophilic organic solvent such as alcohols and especially linear or branched C ₁ -C ₆ monoalcohols, such as ethanol, tert-butanol, n-butanol, isopropanol or n-propanol, and polyols such as glycerine, diglycerine, propylene glycol, sorbitol, pentylene glycol, and polyethylene glycols, or else ethers glycols including C ₂ and hydrophilic C ₂ -C ₄ aldehydes. The aqueous phase may contain all the ingredients conventionally used in a detergent composition and, generally, water-soluble. The detergent composition preferably contains from 10 to 99% by weight of water, preferably more than 20% by weight, and very preferably from 30 to 95% by weight, these percentages being given with respect to the total mass of the composition.

The detergent composition may contain between 1 and 50% by weight of hydrophilic organic solvent as described above. She can also contain between 0.1 and 20% by mass of solid particles. Examples of solid particles that may be determined include inorganic solid particles such as silica or titanium dioxide, organic solid particles such as certain polymers (polyhydroxybutyric acid, polycaprolactone, polyorthoester, polyanhydride), capsules containing additives such as a perfume or a soap. a softener for laundry, said particles generally having a micro-particulate or nano-particle size.

In the context of the invention, apart from the use of the thickening acrylic polymer which is the subject of the invention, the detergent compositions correspond to the compositions traditionally used in this field. For more details, reference may be made to documents FR 2 766 838, FR 2 744 131, EP 0 75996681, US Pat. No. 6,27,439, US 2006/0281660, US Pat. No. 7,773,004 and US Pat. No. 2,334,891, some of which are relevant parts. below.

The composition may also advantageously comprise at least one surfactant. This surfactant may be chosen from anionic, amphoteric, nonionic or canonical surfactants or mixtures thereof. In particular, the composition will comprise a surfactant corresponding to a water-in-oil emulsifier and / or an oil-in-water emulsifier, preferably chosen from those previously mentioned in the context of the polymerization process of the acrylic thickening polymer. In general, the composition will comprise one or more cleaning surfactants.

Surfactants cleansers

when the composition contains one or more cleaning surfactants, these typically represent from 0.1% to 50% by weight, and preferably from 1% to 30% by weight, of the total mass of the composition. The cleaning surfactants which can be incorporated into the composition according to the invention include a variety of nonionic, canonic, anionic and zwitterionic surfactants, such as those described in Cutcheon's detergents and emulsifiers, North American Edition (1996), Al! Ured Publishing Corporation, and in the following documents: FR 2 766 838, FR 2 744 131, GB 2 346 891, US 20060281660, US 6 274 539 and EP 0 759 966, in particular.

In particular, the compositions according to the invention will comprise one or more cleaning surfactants chosen from anionic or nonionic surfactants. The composition may comprise one or more anionic or nonionic cleaning surfactants. The anionic or nonionic cleaning surfactants may be used in an amount such that the total amount of anionic surfactant (s) and / or surfactant (s) nonionic (s) represents from 0.1% to 50% by weight, and preferably from 1% to 30% by weight, of the total mass of the composition.

As examples of anionic cleaning surfactant, mention may be made of:

the alkyl ester sulphonates of formula Ra-CH (S (¼M) -COORb, where Ra represents a C8-C20 alkyl group, preferably a C10-C16 group, Rb a C1-C6 alkyl group, preferably a C1-C3 alkyl group; and M an alkali metal cation (for example a sodium, potassium, lithium cation), a substituted or unsubstituted ammonium (for example, methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylipiperidinium, etc.) or a derivative thereof. an alkanolamine (for example, monoethanolamine, diethanolamine, triethanolamine, etc.), for example the methyl ester sulphonate salts,

Alkylsulfates of formula RCOSO3M ', where Rc represents a C10-C24, preferably C12-C20, and especially C12-C18 alkyl and alkenyl or hydroxyalkyl group, and M' represents a hydrogen atom or a cation of the same as above for M, as well as their ethoxylated (EO) and / or propoxylated (PO) derivatives, having on average from 0.5 to 10 units, preferably from 0.5 to 3 EO and / or OP units; for example, mention may be made of lauryl ether sulfate, and in particular sodium lauryl ether sulphate,

the alkylamide sulphates of formula RdCONHReOSC ^ M "or Rd represents a C2-C22 alkyl group, preferably a C6-C20 alkyl group, Re represents a C2-C3 alkyl group, and M" represents a hydrogen atom or a cation with the same definition as above for M, as well as their ethoxylenated (EO) and / or propoxylenated (PO) derivatives, having on average from 0.5 to 60 EO and / or OP units;

the salts of saturated or unsaturated C8-C24, preferably C14-C20 fatty acids, in particular of the palmite or coconut type, with a cation having the same definition as above for M,

C 8 -C 20 alkylbenzene sulphonates (such as dodecylbenzene sulphonate, especially in its ethanolate form), C 8 -C 22 primary or secondary alkylsulfonates (such as lauryl sulphonate, and in particular sodium lauryl sulphonate), alkylglycerol sulphonates, the sulfonated polycarboxylic acids described in GB 1 082 179, paraffin sulfonates, N-acyl N-alkyl acrylates, alkyl phosphates, isethonates, alkyl sulfonates, alkyl sulfosuccinates, sulfosuccinate monoesters or diesters, N-acyl sarcosinates, sulphates of alkyl glycosides, polyethoxycarboxytates, with a cation having the same definition as above for M.

As examples of non-tonic cleaning surfactant, mention may be made of alkoxy-substituted nonionic surfactants, and in particular:

polyoxyalkylenated alkylphenols (in particular polyethoxyethylenated, polyoxypropylenated or polyoxybutylenated) whose alkyl substituent is in

C6-C12 and containing from 5 to 25 oxyalkylene units; by way of example, mention may be made of the ethoxylated octylphenols sold under the reference TRITON® X, and in particular X95, X-114, X-100 or X-102 by Rohm & Haas Cy, the ethoxylated nonyiphenol, sold under the reference Surfonic® N by Texaco,

polyoxyalkylenated C8-C22 aliphatic alcohols containing from 1 to 25 oxyalkylene units (in particular oxyethylene or oxypropylene); by way of example, mention may be made of the ethoxylated alcohols sold under the tradename Lutensol® by BASF, TER6ITOL® 15-S-9, TERGITOL® 24-L-6 NMW marketed by Union Carbide Corp., NEODOL® 45-9 NEODOL® 23-65, NEODOL® 45-7, NEODOL® 45-4 marketed by Shell Chemical Cy., KYRO EOB marketed by The Procter & Gamble Cy, ICI SYMPERONIC® A3 to A9, PLURONIC® marketed by BASF,

ethoxylated mono- and diglycerides, especially those marketed under the reference Varionic de Wico,

alkoxylated terpene hydrocarbons, such as ethoxylated and / or propoxylated α- or β-pinenes, containing from 1 to 30 oxyethylene and / or oxypropylene units,

The products resulting from the condensation of ethylene oxide or of propylene oxide with propylene glycol, ethylene glycol, in particular of molecular weight in the order of 2,000 to 10,000, such as PLURONIC® marketed by BASF,

the products resulting from the condensation of ethylene oxide or of propylene oxide with ethylenediamine, such as TETRONIC® marketed by BASF,

ethoxylated and / or propoxylated C8-C18 fatty acids containing from 5 to 25 ethoxylated and / or propoxylated units,

ethoxylated fatty amides containing from 5 to 30 ethoxylated units,

ethoxylated amines containing from 5 to 30 ethoxylated units,

the alkoxy-containing amidoamines containing from 1 to 50, preferably from 1 to 25, most preferably from 2 to 20 oxyalkylene units (preferably oxyethylene), and

alkylpoiygtycosides such as alkylpoiygiucosides sold especially under the reference Simulsol® by the company SEPPIC

or the nonionic surfactant (s) present in the compositions according to the invention will have, for example, a HLB value ("Hydrophilic-Lipophilic Balance") of 8 to 13, and preferably of 9, 5 to him.

It is also possible to use other anionic or nonionic surfactants, the hydrophilic part of which contains one or more saccharide units, as described in application FR 2 744 131, which one will be able to refer for more details. It is also possible for the detergent compositions to comprise, instead of or in addition to such anionic or nonionic surfactants, one or more zwitterionic (s) or cationic (s) surfactants. This solution is nevertheless not preferred, since the addition of anionic acrylic thickeners in a composition containing cationic surfactants may lead to incompatibility between the opposite species.

As examples of zwitterionic cleaning surfactant, mention may be made of the Cs-Cw aliphatic quaternary ammonium, phosphonium and sulphonium compounds, which carry a substituent containing an anionic group for solubilization in water, such as a carboxy, a sulfonate, a sulfate, a phosphate, a phosphonate, and the like, alkyl aminosulphonates, alkyl betaines, and alkylamidobetaines (for example, (cocoamylamidopropyl betaine), stearamidopropyldimethylamine, diethylaminoethyl stearamide, dimethyl stearamine, dimethyl , soyamamine, myrtstyiamine, tridecylamine, ethylstearylamine, N-tallowpropanediamine, ethoxyfine stearylamine (5 moles of ethylene oxide), dihydroxyethylstearylamine, rarachidylbéhenylamine, and the like.

As an example of a cationic cleaning surfactant, mention may be made of quaternary ammonium salts having three lower (C 1 to C 4) alkyl groups (preferably methyl groups) and a long-chain (C 8 to C 20) alkyl group. for example (coconut) trimethylammonium chloride; alkylpyridinium salts and other compounds in which the nitrogen atom of pyridine takes a quaternary form, for example as in an alkylpyridinium bromide, preferably with C 10 -C 10 alkyl chains, t preferably C12 to C18.

The detergent compositions according to the invention will also contain, most often, one or more additives chosen from: detergency builders (also called "builders"), antifouling agents, anti-redeposition agents, bleaching agents, fluorescers (also called optical brighteners), suds suppressors (also called antifoam agents), enzymes, chelating agents, neutralizing agents and pH adjusting agents. In particular, the detergent compositions according to the invention will comprise at least one cleaning surfactant and at least one detergency builder (also called "builders"), especially in the case of dishwashing compositions, for dishwashers. Of course, these additives will be adapted by those skilled in the art, depending on the intended application for the detergent composition.

Such additives are described in particular in FR 2766838 and FR 2744131 and their description is repeated below:

Adjuvant Detergecne (also named "builders")

Such detergents, also known as "builders", are counting agents that make it possible to complex the ions of the water which have a detrimental effect during cleaning, in particular in the case of cleaning with hard water. Such an agent will, in particular, be incorporated in compositions for cleaning dishes, for dishwashers.

The composition may comprise one or more detergency builder (s). The detergency builders may be inorganic or organic in nature. They may be used in an amount such that the total amount of detergency builder (s) is of the order of 5 to 50% by weight of the total mass of the composition. As examples of detergency builder, mention may be made of:

polyphosphates (tripolyphosphates, pyrophosphates, orthophosphates, hexametaphosphates) of alkali metals, ammonium or alkanolamines,

tetraborates or borate precursors,

alkali or alkaline earth carbonates (bicarbonates, sesquicarbonates),

the lamellar silicates described in patent US 4664839, Crystalline or amorphous aluminosilicates of alkali metals (sodium, potassium) or of ammonium, such as the oleoliths A, P, X,

- thy water-soluble polyphosphonates (ethane 1-hydroxy-1- diphosphonate, methylene diphosphonate salts, ...) _/

- polycarboxylate ethers (oxydisuccinic acid and its salts, monosuccinic acid tartrate and its salts, acidic disartonic tartrate and its salts ··.),

the hydroxypolycarboxylate ethers,

citric acid, mellitic acid, succinic acid and their salts, for example sodium citrate,

- ies salts of polyacetic acids (éthvlènediaminetetraacétates, nitritotriacétates, S- (2 hydroxyethyl) nitrilodiacetates ...) _<

the C5-C20 alkyl succinic acids and their seis (2-dodecenylsuccinates, laurylsucnates, etc.),

polyacetal carboxylic esters,

polyaspartic acid, pdyglutamic acid and their salts,

the potyimides derived from the polycondensation of aspartic acid and / or of glutamic acid,

polycarboxymethyl derivatives of giutamic acid (as N, Nbis (cartx> xymethyl) glutamic acid and its salts, especially its sodium salt, etc.) or other amino acids,

aminophosphonates such as nitrilotris (methylene phosphonates), and

polyfunctional aromatic compounds such as dihydroxydisulfobenzenes.

Anti-fouling

The composition may comprise one or more antifouling agent (s), they may be used in an amount such that the total amount of antifouling agent (s) is from 0.01 to 10%, especially 0.2 at 3%, by weight of the total mass of the composition. As examples of antifouling agent, mention may be made of:

cellulose derivatives such as hydroxyethers of cellulose, methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, hydiOxybutyl methylcellulose,

polyvinyl esters grafted onto polyalkylene trunks such as polyvinyl acetates grafted onto polyoxyethylene trunks (as described, for the most part, in EP 0 219 048),

- your polyvinyl alcohols,

polyester copolymers based on ethylene terephthalate and / or propylene terephthalate and polyoxyethylene terephthalate units, with a molar ratio: number of ethylene terephthalate and / or propylene terephthalate units / number of polyoxyethylene terephthalate units of 1/10 to 10/1, preferably from 1/1 to 9/1, the polyoxyethylene terephthalates having polyoxyethylene units having a molecular weight of from 300 to 5000, preferably from 600 to 5000 (as described in particular in US 3,959,230, US 3,893,929, US 4,116,896, US 4,702,857 and US 4,770,666);

Sulphonated polyester oligomers obtained by sulphonation of an oligomer derived from ethoxylated aliphatic alcohol, dimethyl terephthalate and 1,2-propylene diol, having from 1 to 4 sulphonated groups (as described in particular in US 4,968,451),

the polyester copolymers based on propylene terephthalate and polyoxyethylene terephthalate units and terminated with ethyl or methyl units (as described in particular in US Pat. No. 4,711,730) or polyester oligomers terminated with alkylpolyethoxy groups (as described in particular in US 4,702,857); or sulfopolyethoxy anionic groups (as described in particular in US 4,721,580) or sulfoaroyls (as described in particular in US 4,877,896),

sulfonated polyesters having a number-average molecular weight of less than 20,000, obtained from a diester of terephthalic acid, a diester of sulphoisophthalic acid and a diol (as described in particular in FR 2 720 400) , and

polyesters-polyurethanes obtained by reaction of a polyester of molecular mass in a number of 300-4000 obtained from acid adipic acid and / or terephthalic acid and / or sulfoisophthalic acid and a diol, on a prepolymer with terminal isocyanate groups obtained from a polyoxyethylene glycoi with a molecular weight of 600-4000 and a diisocyanate (as described in particular in FR 2 334 698).

The composition may comprise one or more anti-redeposition agents. They may be used in an amount such that the total amount of anti-redeposition agent (s) represents from 0.01 to 10%, especially from 0.01 to 5% by weight of the total mass of the composition. As examples of anti-redeposition agents, mention may be made of:

ethoxylated monoamines or polyamines, ethoxylated amine polymers (as described in particular in US Pat. No. 4,597,898 and EP 11,984),

carboxymethylcellulose,

sulphonated polyester oligomers obtained by condensation of isophthalic acid, dimethyl sulphosuccinate and diethylene glycol (as described in particular in FR 2,236,926), and

polyvinylpyrollidones.

Bleaching agents

The composition may comprise one or more bleaching agents. They may be used in an amount such that the total amount of bleaching agent (s) is from 0.01% to 20%, especially from 1% to 10% by weight of the total mass of the composition. As examples of bleaching agents, mention may be made of:

perborates, such as sodium perborate monohydrate or tetrahydrate,

chlorine bleaching agents, such as hypochlorite, especially an alkali metal, for example sodium hypochlorite (bleach), which also have a cleaning and disinfecting role,

peroxygen compounds such as sodium carbonate peroxyhydrate, pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide, sodium persulfate, diphenoyl peroxide, and

percarboxylic acids and their sets (called "percarbonates") such as magnesium monoperoxyphthalate hexahydrate, magnesium metachloroperbenzoate, 4-nonylamino-4-oxoperoxybutyric acid, 6-nonylamino-6-oxoperoxycaproic acid, diperoxydodecanedioic acid , nonyiamide of peroxysuccinic acid, decyldiperoxysuccinic acid and phthalimidoperoxyhexanoic acid. when the composition comprises one or more bleaching agents, it will also preferably comprise a bleaching activator generating in situ in the medium tessivial, a carboxylic peroxyacid; among these activators, mention may be made of tetraacetylethylene diamine, tetraacetyl methylene diamine, tetraacetyl glycoluryl, sodium p-acetoxybenzene sulfonate, glycerol trialkalates such as pentaacetyl glucose and octaacetyl lactose, etc.

Fluorescence agents

The composition may comprise a single or more fluorescent agent (s), particularly when the composition is a laundry detergent. They may be used in an amount such that the total amount of fluorescent agent (s) represents from 0.05 to 1.2% by weight of the total mass of the composition. As examples of fluorescent agent, mention may be made of: derivatives of stiibene, pyrazoline, coumarin, fumaric acid, cinnamic acid, azoles, methine, cyanines, thiophenes, etc.

Agetns 'suppressor' foam

The composition may comprise one or more suds suppressor (s), particularly when the composition is a laundry detergent. They may be used in an amount such that the total amount of suds suppressor (s) is from 0.01 to 5% by weight of the total mass of the foam. composition. By way of examples of suds suppressing agent, mention may be made of:

- monocarboxylic fatty acids C10-C24 or their alkaline salts, their ammonium or alkariolamine salts, triglycerides of fatty acids,

^• saturated or unsaturated aliphatic, alicyclic, aromatic or heterocyclic hydrocarbons, such as paraffins and waxes,

N-alkylaminotriazines,

monostearylphosphates, monostearyl alcohol phosphates, and polyorganosiloxane oils or resins optionally combined with silica particles.

enzymes

The composition may comprise one or more enzyme (s), particularly when the composition is a laundry detergent. They may be used in an amount such that the total amount of enzyme (s) represents from 0.005 to 0.5% by weight of the total mass of the composition. Examples of enzymes that may be mentioned include proteases (for example Alcalase or Savinase, marketed by Novo Nordisk), amylases, lipases, cellulases and peroxidases.

Chelating agents

By way of example of chelating agents which can be incorporated in the composition, mention may be made of ΙΈΟΤΑ (ethylenediaminetetraacetic acid) and the salts thereof, such as ΙΈ0ΤΑ disodium; cyclodextrins; and their analogues. When the composition contains one or more chelating agents, it (s) typically represents from 0.001% to 3% by weight, of the total mass of the composition, preferably from 0.01% to 2% by weight, and preferably from 0.01% to 1% by weight, of the total mass of the composition.

Thickening polymers

One or more thickening polymers, other than the acrylic polymers previously described, may also be incorporated In the detergent compositions according to the invention, these polymers may be natural, semi-natural or synthetic polymers.

Among the natural polymers, mention may be made of chitin, chitosan and their derivatives, gum arabic, agar, guar gum, locust bean gum, gum gum, karaya gum, xanthan gums and alginates.

Among your synthetic polymers, mention may be made of polymers based on acrylamide, sodium acrylate, vinylpyrrolidone or 2-acrylamido-2-methylpropanesulphonic acid, for example obtained by other polymerization processes than that described in the context of the invention, and in particular by precipitation polymerization.

Neutralization agents and pH adjusting agents

One or more neutralizing agents and / or one or more pH adjusting agents may be included in the composition to bring the pH of the composition to the desired levels. Examples of neutralizing agents and pH adjusting agents include triethanolamine, aminomethylpropanol, ammonium hydroxide, sodium hydroxide, other alkali hydroxides, alkali metal silicates, such as sodium carbonate, alkali silicates such as sodium silicate, ascorbic acid and salts thereof, sorbic acid and salts thereof, phosphoric acid and salts thereof. it, citric acid and salts thereof, lactic acid and salts thereof, glycolic acid and salts thereof, boric acid and salts thereof. here, acetic acid and salts thereof, and their analogues. Preferably, the neutralizing agent (s) and the pH adjusting agent (s) are used in the composition of the invention in an amount sufficient to provide a pH ranging from 4 to 10. pH adjustment agents are used) in an amount sufficient to give the composition a pH ranging from 4.5 to 8, and preferably from 5 to 7.5.

The detergent compositions may also comprise other additives such as: ^• a softening agent such as clay ies, for example in an amount such that the total amount of agent (s) softeners) represents from 0.5 to 10% by weight of the total weight of the composition

a buffer or pH-modifying agent,

- A conservationist,

- a perfume,

an opacifying agent,

- a dye,

- a pearling agent ...

The following examples illustrate the invention, but are not limiting in nature.

I. Free from Preparation of Homopolymer Based on Acrylic Acid / Sodium Acrylyte

Exempt%:

The ingredients of the aqueous phase are loaded into a 1 L beaker with magnetic stirring:

-150 g of glacial acrylic acid

-605 g of deionized water

0.023 g of sodium hypophosphtte (150 ppm / total mass of monomers)

-0.10 g of sodium diethylenetriaminepentacetate

0.075 g of methylenebisacrylamide (500 ppm / total mass of monomers)

-0.15 g of sodium bromate

Then, in a 1 L glass reactor, with mechanical stirring, the organic phase is prepared with:

• 102 g of aliphatic hydrocarbon (Isopar L)

-98 g of white mineral oil (Marcol 152)

-20 g of sorbitol monooleate

25 g of polymeric stabilizer (Hypermer 1083). The aqueous phase is gradually transferred to the organic phase. The pre-emulsion thus formed is then subjected to high shear for 1 minute (Ultra Turrax, IKA).

The inverse emulsion is then degassed for 30 minutes by simply sparging with nitrogen.

An aqueous solution containing 1.0% by weight of sodium metabisulphite is then added at a flow rate of 2.5 ml / h for a period of 1h30. Once the maximum temperature is reached, the temperature of the reaction mixture is maintained for 60 minutes before cooling.

Finally, 40 g of ethoxylated tridecyl alcohol (6 mol) are added around 30 ° C.

Exempt 2:

The ingredients of the aqueous phase are loaded into a 1L beaker with magnetic stirring:

-175 g of glacial acrylic acid

-580 g of deionized water

-0.026 g of sodium hypophosphite (150 ppm / total mass of monomers)

-0.10 g of sodium diethylenetriaminepentacetate

0.077 g of methylenebisacrylamide (500 ppm / total mass of monomers)

-0.15 g of sodium bromate

Then, for the preparation of the organic phase and the rest of the preparation process, the procedure is as in Example 1.

Example 3

• 100 g of glacial acrylic acid

-655 g of deionized water 0.015 g of sodium hypophosphite (150 ppm / total mass of monomers)

• 0.109 of sodium diethylenetriaminepentacetate -0.05 g of methyleneblsacryiamide (500 ppm / total mass of monomers)

-0 _/ 15 g of sodium bromate

Then, for the preparation of the organic phase and the remainder of the preparation process, the procedure is as in Example 1.

Example 4: Neutralization 3.5% / Concentration 2.76

The same procedure as in Example 1 is carried out by adding to the aqueous phase 5.83 g of 50% sodium hydroxide solution, while maintaining the same weight of aqueous phase by adjusting the amount of deionized water.

Example 5: Netization 19% / concentration 3.5

-190 g of glacial acrylic acid

-40 g of 50% sodium hydroxide solution

-525 g of deionized water

-0.028 g of sodium hypophosphite (150 ppm / total mass of monomers)

-0.10 g of sodium diethylenetriaminepentacetate -0.095 g of methylenebisacryiamide (500 ppm / total mass of monomers)

0.15 g of sodium bromate

Example, Comparative 1:

-50 g of glacial acrylic acid -705 g of deionized water

-0.075 g of sodium hypophosphite (150 ppm / total mass of monomers)

• 040 g of sodium diethylenetriaminepentacetate

0.043 g of methylenebisacrylamide (860 ppm / total weight of monomers)

-0.15 g of sodium bromate

Then, for the preparation of the organic phase and the remainder of the preparation process, the procedure is carried out in accordance with Example 1.

Compared with:

-199 g of glacial acrylic acid

-115 g of 50% sodium hydroxide solution

-441 g of deionized water

0.03 g of sodium hypophosphite (150 ppm / total mass of monomers)

-0.10 g of sodium diethylenetriaminepentacetate

0.15 g of methylenebisacrylamide (750 ppm / total mass of monomers)

-0.15 g of sodium bromate

Comparative Example 3

-199 g of glacial acrylic acid

-556 g of deionized water

• 0.03 g of sodium hypophosphite (150 ppm / total mass of monomers)

-0.10 g of sodium diethylenetriaminepentacetate 0.1 g of methylenebisacrylamide (500 ppm / total mass of monomers)

-0.15 g of sodium bromate

Then, for the preparation of the organic phase, the procedure is as in Example 1.

the aqueous phase is progressively transferred into the organic phase. The pre-emulsion thus formed is then subjected to high shear for 1 minute (Ultra Turrax, IKA).

An aqueous solution containing 1.0% by weight of sodium metabisulphite is then added at a flow rate of 2.5 ml / h. Immediately after the beginning of the addition of this reducing solution, the emulsion is destabilized and then coagulates. Polymerization is impossible, the system is not stable.

Comparative Example 4

-150 g of glacial acrylic acid

-83 g of 50% sodium hydroxide solution

-522 g of deionized water

0.023 g of sodium hypophosphite (150 ppm / total mass of monomers)

-0.10 g of sodium diethylenetriaminepentacetate

0.75 g of methylenebisacrylamide (500 ppm / total mass of monomers)

-0.15 g of sodium bromate

Then, for the preparation of the organic phase and the rest of the preparation process, the procedure is as in Example 1. Characterization of polymers

Procedure: Measurement of the viscosity of the aqueous iso-concentration polymer solution [0.16% by mass]

400 g of deionized water are introduced into a 400 ml beaker and then, with mechanical stirring (tripnel - 500 rpm), the desired amount of inverse emulsion is gradually added to obtain a solution containing 0.16% by weight The pH is then adjusted to 7 +/- 0.1 with sodium hydroxide. At this pH, 100% of the acid functions present on the polymer are neutralized. The solution is left stirring for 15 minutes and then for 5 minutes at rest. The viscosity is then measured using an RVT type Brookfield viscometer with the module 4 and rotation speed 20 rpm.

The results are shown in Table 1.

Table l

Example NFA CM I Viscosity 0.16% in water (cps)

1 i i 0% 2,8 1 6500

2 1 0% 3.2 4000!

1 3 0% L ?. 6200

! 4 3.5% 2.8 6500

\ 5 i 19% 3.5 2500

1 Comparative 1! 0% 0.9 Ϊ70Ό]

I Gompàriaf 2 1 52% 3.7 500

1 Q> mpàra¾f 3 | 0% ¾7 î Unstable emuision! 1 Comparative 4 \ 50% 2.8 1500

NFA: Neutralization of acid functions (%) after polymerization

CM: Concentration of monomer in mmol / g of aqueous phase

The polymers used in the context of the invention obtained by the inverse emulsion polymerization process have a thickening effect which is much greater than the polymers obtained by inverse emulsion processes which do not satisfy the conditions of% neutralization before polymerization and concentration of monomers. . The polymers obtained according to the invention are very effective at very low concentration.

Resistance to surfactants is evaluated by using these same polymers in deionized water and in the presence of a surfactant: sodium lauryl ether sulphate (LES), marketed by BASF under the Texapon® NSO reference.

The polymers are compared with each other and with other commercially available thickening polymers: Acusol® 820 (Rhom & Haas), an anionic copolymer based on ethyl acrylate and acrylic acid and containing a hydrophobic monomer, obtained by polymerization in emulsion (not inverse) and Carbopol® 676 (Lubrizol), a crosslinked acrylic acid polymer obtained by precipitation polymerization. These commercial products are typically used in detergent compositions as a thickening agent.

The evolution of the viscosity of a solution comprising 1% by weight of thickening polymer is studied, as a function of the concentration of LES.

More precisely in a beaker of 400 ml 250 g of deionized water are introduced, then under mechanical stirring (tripâle - 500 revolutions per minute), the quantity of inverse emulsion desired is gradually added to obtain a solution containing 1% by mass of thickening polymer. The pH is then adjusted to 7 +/- 0.1 with sodium hydroxide. At this pH, 100% of the acid functions present on the polymer are neutralized. The LES is added to the desired concentration. The solution is left stirring for 15 minutes and then for 5 minutes at rest. The viscosity is then measured using a Brookfleld type RVT viscometer with the module 4 and a rotational speed of 20 rpm. The results obtained as a function of the added weight% of LES are recorded in Table 2. Table 2 - Viscosity measurement of a solution containing 1% by weight of polymer with the addition of sodium lauryt ether sulphate (LES)

NFA: Neutralization of acid functions (%) after polymerization

CM: Concentration of monomer in mmol / g of aqueous phase Table 3 - Percentage drop in viscosity with the addition of sodium iuryl ether sulphate (LES).

The percentage of viscosity drop corresponds to the ratio between the initial viscosity of the thickened solution without addition of surfactant minus the viscosity of the solution with addition of the surfactant, on the initial viscosity multiplied by 100.

The polymers of Examples 1 to 5 make it possible to obtain a lower drop in viscosity and therefore good resistance to surfactants compared with the polymers of Comparative Examples 1 to 4 and Carbopol® 676 and Acusol® 820.

The person skilled in the art can easily, thanks to his knowledge, find the best compromise between thickening efficiency and resistance to surfactants by varying polymerization parameters.

H - Polymer behavior in the presence of different surfactants

The following series of tests consists in evaluating the viscosity of the solutions of the polymers according to the invention in the presence of different surfactants commonly used in detergent compositions. The same procedure that resulted in the results in Table 2 is implemented. The mass% by weight of any surfactant is 5% (relative to the total mass of the solution).

Table 4 - Viscosity measurement of a solution containing 1% by weight of polymer with addition of 5% by weight of different surfactants.

Ex Lauryl Simulsol SL 8 I Lauryl sulphonate

ether (SEPPIC - sodium

alkylpoly-sodium sulphate giucoside)

1 12500 18500 111000

2 9000! 15500 1 8700 1

3 12500 17500! 10500

^" 4 ΓΜκ) Ï8500 t ^' Issoo

ΓΪ3000! TIÏ500 I

Comp.i loe6] ^" oooooo _

Comp.2 15500 124000 | 5000

Comp.3! NA NA j NA

Comp.4 I 3800 15000 2900

Carbopol® j 18500 36000 1 17000

676

Acusol <E> (400 5700 to 300)

Table 5 - Percentage drop in viscosity with the addition of 5% by weight of the various surfactants.

The percentage of viscosity drop corresponds to the ratio of the so-called initial viscosity of the thickened solution without addition of surfactant to the viscosity of the solution with addition of the surfactant, to the initial viscosity multiplied by 100.

Table 5 continued

| Ex; Dodecyl I LutensolTO j Alpha-step MC-48 (Stepan j

! benzene 89 (alcohol) - methyl ester sulphonate |

1 sodium ethoxylated sulphonate)

I sodium j

11 days-43% | -10% 1 -42%

| 2; -52% j-11%; -50%

| 3 | -39% | -10% j -38% j

| 4 -12% | -45%

| 5 | -52% | -14% 1 -52%

i Comp.l j-78% | -27%! -77%

1 Comp.2 i-84% | -22% | -84%

j Comp.3! NA j NA j NA

1 Comp.4 d -84% | -22% j -83%

| Carbopol® 676 ï-62% | -20% 1 -62%

I Acusoi ® 820 i-96% 1-31% 1-95%

The polymers of Examples 1 to 5 make it possible to obtain a very good resistance to surfactants compared to the polymers of Comparative Examples 1 to 4 and to Carbopol® 676 and Acusol® 820, with different surfactants.

III - Efficacy in detergent compositions

The following tests show the advantage of using the polymers obtained under the conditions of concentration and% of neutralization defined in the context of the invention in detergent compositions: Such polymers provide good thickening of the compositions and good resistance to them. presence of surfactants.

Laundry detergent is formulated with the inverse emulsion of Example 1 or with the Acusol ® 820, a market reference in this type of formulation. A detergent product for dishwashers is formulated with the inverse emulsion of Example 3 and Carbopol® 676, market reference in this type of formulation.

For each of the compositions numbered 1 and 2 below, the preparation protocol applied is as follows:

Composition Nº1: Laundry detergent

This formulation corresponds to a basic liquid detergent whose viscosity is controlled by the presence of an acrylic polymer. The assay is adjusted to obtain a viscosity of 800 cps +/- 200 cps (Brookfieid RVT, 20 rpm, sp 3)

The preparation procedure is simple, it consists in adding in the order presented in Table 6 below, all the ingredients of the following formulation in a 400 ml beaker to obtain 250 g of solution in the end:

Table 6

* The acrylic polymers tested are as follows:

The polymer of Example 1 makes the laundry formulation containing 23% surfactant much more effective than Acusol® 820.

Composition # 2: Liquid Dishwasher Product

This formulation corresponds to an opaque liquid gel "javellisé for washing machine whose viscosity is controlled thanks to the presence an acrylic polymer. The dosage is adjusted to obtain a viscosity of 9000 cps +/- 2000 cps (Brookfield RVT, 20 rpm, sp 6)

The preparation procedure is simple, it consists in adding in the order presented in Table 7 below, all the ingredients of the following formulation in a beaker of 400 ml, to obtain 250 g of solution in the end:

3% lauryl sulphate; Add slowly and leave under 1 sodium (surfactant) stirring for 5 minutes. ■ Sodium nypc iorlte (at 8%) Cool the viscous solution to 12.5% by mass at a temperature <30 ° C then aqueous solution I add the bleach.

I Leave stirring for 15 minutes * The acrylic polymers tested are as follows

The polymer of Example 3 allows the laundry formulation to be thickened much more effectively for laundry containing 3% by weight, compared to Carbopoi® 676.

Claims

CLAIMS:

1 - Use, for the manufacture of a liquid aqueous detergent composition for household or industrial use, of a branched or cross-linked polymer composed of the repetition of one or more monomeric units, with at least one of the monomeric units which corresponds to a monomer comprising an acrylic group and at least 30 mol% of the monomeric units which carry at least one weak acid function, optionally in neutralized form, said polymer being obtained:

ii) during the polymerization, at most 20% of the acid functions present on the monomers having at least one acid function are in neutralized form.

2 - Use, for thickening a liquid aqueous detergent composition for household or industrial use, of a branched or crosslinked polymer composed of the repetition of one or more monomeric units, with at least one of the monomeric units which corresponds to a monomer comprising a acrylic group and at least 30 mol% of the monomeric units which carry at least one weak acid function optionally in neutralized form, said polymer being obtained: by polymerization of an aqueous solution of one or more monomers in water-in-oil inverse emulsion, at least one of the monomers used being an acrylic monomer and one or more of the monomers used being a monomer carrying at least one weak acid function, the molar percentage of monomers carrying at least one weak acidic function with respect to all the monomers used being at least 30%, the aqueous phase containing at least one monomer acting as a branching agent, so that the polymerization leads to a plugged or cross-linked polymer, characterized in that:

3 - Use according to claim 1 or 2 characterized in that the polymer comprises a percentage of neutralized acid functions of 30 to 100% relative to all the acid functions present on the polymer, obtained by a step of at least partial neutralization of the acid functions present on the polymer made after the polymerization, but before or after the preparation of the composition.

4 - A detergent liquid aqueous composition for household or industrial use comprising at least one branched or crosslinked polymer composed of the repetition of one or more monomeric units, with at least one of the monomeric units which corresponds to a monomer comprising an acrylic group and at least one 30 mol% of the monomeric units which carry at least one weak acid function at least partially in neutralized form, the percentage of acid functions neutralized with respect to all the acid functions present on the polymer being from 30 to 100%, said polymer being obtained: by polymerization of an aqueous solution of one or more monomers in water-in-oil inverse emulsion, at least one of the monomers used being an acrylic monomer and one or more of the monomers used being a monomer carrying at least one weak acid function, the molar percentage of monomers carrying at least one weak acid function with respect to all the monomers used being at least 30%, the aqueous phase containing at least one monomer acting as a branching agent, so that the polymerization leads to a plugged or cross-linked polymer, characterized in that:

the polymerization being followed by a step of at least partial neutralization of the acid functions present carried out before or after the incorporation of the polymer into the composition.

5 - Composition according to claim 4 in the form of a solution, gel or dispersion.

6 - Use of a composition according to claim 4 or 5 for cleaning textile fibers, in particular for washing clothes manually or in a washing machine, or for cleaning a hard surface such as dishes, furniture, clothes , panes, bowls or metals, in particular for cleaning dishes manually or in dishwashers.

7 - Use according to claim 1, 2, 3 or 6 or composition according to claim 4 or 5 characterized in that, during the polymerization, at most 10%, preferably at most 5%, and preferably at most 2%, Acid functions present on the monomers having at least one acid function are in neutralized form. 8 - Use according to one of claims 1 to 3, 6 and 7 or composition according to claim 4, 5 or 7 characterized in that all the acid functions present on the monomers are in free acid form, during the polymerization.

9 - Use according to one of claims 1 to 3 and 6 to 8 or composition according to claim 4, 5, 7 or 8 characterized in that the polymerization is carried out with a concentration of all the monomers in aqueous solution belonging to the range of from 1.7 to 3.3 mmol per gram of aqueous solution.

10 - Use according to one of claims 1 to 3 and 6 to 9 or composition according to one of claims 4, 5 and 7 to 9 characterized in that the polymer comprises a molar percentage of monomeric units carrying one or several weak acid function (s), with respect to all the monomeric units carrying an acid function, of at least 50%, preferably at least 70%, very preferably at least 80%.

11 - Use according to one of claims 1 to 3 and 6 to 10 or composition according to one of claims 4, 5 and 7 to 10 characterized in that all the monomers used for the preparation of the polymer are monomers having at least ethylenic unsaturation.

12 - Use according to one of claims 1 to 3 and 6 to li or composition according to one of claims 4, 5 and 7 to 11 characterized in that the monomeric unit (s) carrier (s) at least one weak acid function, in free form, is (are) chosen from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid and acid. fumaric, acrylic acid being preferred.

13 - Use according to one of claims 1 to 3 and 6 to 12 or composition according to one of claims 4, 5 and 7 to 12 characterized in that the polymer is a copolymer comprising at least one neutral monomeric unit selected from i acrylamide, methacrylamide, Ν, Ν-dimethylacrylamide, N-vinylmethylacetamide, N-vinylformamide, vinyl acetate, diacetoneacrylamide, N-Isopropylacrylamide, N-t-hydroxy-1,1-bis (hydroxymethyl) ethyl] propenamide, (2-hydroxyethyl) acrylate, (2,3-dihydroxypropyl) acrylate, methyl methacrylate, (2-hydroxyethyl) methacrylate, (2,3-dihydroxypropyl) methacrylate and vinylpyrrolidone.

14 - Use according to one of claims 1 to 3 and 6 to 13 or composition according to one of claims 4, 5 and 7 to 13 characterized in that all the monomeric units carrying at least one acid function present in te polymer are monomeric units carrying one or more weak acid functions.

15 - Use or composition according to claim 14 characterized in that the polymer present in the composition is an acrylic acid / acrylamide copolymer with from 30 to 100% of the functions acrylic acid in neutralized form.

16 - Use according to one of claims 1 to 3 and 6 to 13 or composition according to one of claims 4, 5 and 7 to 13 characterized in that the polymer is a copolymer comprising at least one monomeric unit carrying a or more function (s) strong acid.

17 - Use or composition according to claim 16 characterized in that te molar percentage in monomeric units carrying one or more strong acid function (s) with respect to all the monomeric units is less than 50%, and preferentially lower than 30%.

18 - Use or composition according to claim 16 or 17 characterized in that the monomeric unit (s) carrier (s) of one or more strong acid function (s), in free form, is (are) selected from acrylamidoalkylsulfonic acids such as 2-acrylamido-2-methylpropane sulfonic acid.

19 - Use or composition according to claim 16, 17 or 18 characterized in that the polymer present in the composition is a 2-acryiamido-2-methylpropane sulfonic acid / acidic copolymer acrylic or 2-acrylamido-2-methylpropane sulfonic acid / acrylic acid / acrylamide, with from 30 to 100% of the acid functions present on the polymer which are in neutralized form.

20 - Use according to one of claims 1 to 3 and 6 to 19 or composition according to one of claims 4, 5 and 7 to 19 characterized in that the branching agent is selected from methylenebisaciylamide (MBA), ethylene glycol dl-acrylate, polyethylene glycol dlmethacrylate, diacryiamide, cyanomethylacrylate, vinyloxyethylacrylate, vinyloxymethacrylate, triallylamine, formaldehyde, glyoxal, glycidyl ethers such as ethylene glycol diglycidyl ether, epoxies and mixtures thereof.

21 - Use according to one of claims 1 to 3 and 6 to 20 or composition according to one of claims 4, 5 and 7 to 20 characterized in that the amount of branching agent is between 5 and 10 000 ppm in mass relative to the total mass of monomers, and preferably between 100 and 5000 ppm.

22 - Use according to one of claims 1 to 3 and 6 to 21 or composition according to one of claims 4, 5 and 7 to 21 characterized in that the polymerization reaction is conducted in the presence of a water emulsifier in oil.

23 - Use according to one of claims 1 to 3 and 6 to 22 or composition according to one of claims 4, 5 and 7 to 22 characterized in that the polymerization is conducted with a transfer agent selected from methanol, l isopropyl alcohol, sodium hypophosphite, 2-mercaptoethanol, sodium methailysulfonate and mixtures thereof.

24 - Use or composition according to claim 23 characterized in that the amount of transfer agent is between 0 and 5000 ppm by weight relative to the total mass of monomers, and preferably between 10 and 2500 ppm.

25 - Use according to one of claims 1 to 3 and 6 to 24 or composition according to one of claims 4, 5 and 7 to 24 characterized in that the polymerization is followed by one or more of the following steps:

a dilution or a concentration of the emulsion obtained,

an insulation to obtain the polymer in the form of a powder. 26 - Use according to one of claims 1 to 3 and 6 to 25 or composition according to one of claims 4, 5 and 7 to 25 characterized in that the polymer plugged or crosslinked into the composition has a viscosity at 0 , 16% by weight in demineralized water whose pH is adjusted to 7 +/- 0.1 with sodium hydroxide, measured at 25 ° C. with a Brookfield RVT apparatus (rotational speed 20 t / min), belonging to the range from 2000 mPa.s to 100 000 mPa.s, in particular to the range from 3000 mPa.s to 50 000 mPa.s.

27 - Use according to one of claims 1 to 3 and 6 to 26 or composition according to one of claims 4, 5 and 7 to 26 characterized in that the composition comprises from 0.01% to 10% by weight of polymer acrylic branched or crosslinked, with respect to the total mass of the composition, and preferably from 0.1 to 5% by weight of branched or crosslinked acrylic polymer.

28 - Use according to one of claims 1 to 3 and 6 to 27 or composition according to one of claims 4, 5 and 7 to 27 characterized in that the composition comprises one or more surfactant (s), preferably chosen (s) among the anionic and nonionic cleaning surfactants.

29 - Use or composition according to claim 28 characterized in that the composition comprises from 0.1% to 50% by weight of surfactant (s), preferably chosen from anionic and nonionic cleaning surfactants, by relative to the total mass of the composition, and preferably from 1% to 30% by weight of surfactant (s), preferably chosen from anionic and nonionic cleaning surfactants. 30 - Use or composition according to claim 28 or 29 characterized in that the composition comprises one or more surfactant (s) cleanser (s), chosen (s) from:

Anionic surfactants chosen from:

the sulphonated alkyl esters of formula Ra-CH (SO 3 M) -COORb, where Ra represents a C 8 -C 20 alkyl group, preferably a C 10 -C 16 alkyl group, Rb a C 1 -C 6, preferably C 1 -C 3, alkyl group, and M an alkaline cation, a substituted or unsubstituted ammonium or an alkanolamine derivative,

alkylsulfates of formula RCOSO3M ', where Rc represents a C10-C24 alkyl, aenenyl or hydroxyalkyl group, preferably a C12-C20, and especially C12-C18, and M' represents a hydrogen atom or a cation of the same as above for M, and their ethoxylated (EO) and / or propoxylated (PO) derivatives, having on average 0.5 to 10 units, preferably 0.5 to 3 EO and / or OP units,

the alkylamines sulphates of formula RdCONHReOSOjM "where Rd represents a C2-C22 alkyl group, preferably a C6-C20 alkyl group, Re represents a C2-C3 alkyl group, and M" represents a hydrogen atom or a cation of the same definition above for M, as well as their ethoxylated (EO) and / or propoxylated (PO) derivatives, having on average from 0.5 to 60 EO and / or OP units;

the salts of saturated or unsaturated C8-C24, preferably C14-C20, fatty acids, in particular of the palmite or coconut type, with a cation having the same definition as above for M,

C8-C20 atkylbenzenesulfonates, C8-C22 primary or secondary alkylsulfonates, alkylglycerol sulfonates, sulfonated polycarboxylic acids, paraffin sulfonates, N-acyl N-alkyltaurates, alkylphosphates, isethionates, alkylsuccinates, alkylsuifosuccinates, monoesters or diesters of sulfbuccinates, N-acylsarcosinates, sulfates of alkyl glycosides, polyethoxycarboxylates, with a cation having the same definition as above for M; and

• the nonionic tensts, chosen from:

polyoxyalkylene alkyiphenols whose alkyl substituent is C 6 -C 12 and containing from 5 to 25 oxyalkylene units,

Polyoxyalkylenated C8-C22 aliphatic alcohols containing from 1 to 25 oxyalkylene units (in particular oxyethylene or oxypropylene);

the mono and diglycerols, ethoxylated,

alkoxy-terpene hydrocarbons, such as ethoxylated and / or propoxylated α- or β-pinenes containing from 1 to 30 oxyethylene and / or oxypropylene units,

^• products resulting from condensing ethylene oxide or protoxide of propylene copolymer with propylene glycol, ethylene glycol, including molecular weight of the order of

2000 to 10000,

the products resulting from the condensation of ethylene oxide or of propylene oxide with ethylene diamine,

ethoxylated fatty amides containing from 5 to 30 ethoxylated units,

ethoxylated amines containing from 5 to 30 ethoxylated units,

alkoxylated amidoamines containing from 1 to 50, preferably from 1 to 25, especially from 2 to 20 oxyalkylene units (preferably oxyethylene), and

alkylpotyglycosides such as allcylpolyglucosides.

31 - Use according to one of claims 1 to 3 and 6 to 30 or composition according to one of claims 4, 5 and 7 to 30 characterized in that the composition comprises at least one additive selected from: detergency adjuvants also called " bulldozer agents, anti-fouling agents, anti-redeposition agents, bleaching agents, fluorescers, suds suppressors, enzymes, chelating agents, neutralizing agents and pH adjusting agents.

32 - Use according to one of claims 1 to 3 or 6 to 31 or composition according to one of claims 4, 5 and 7 to 31 characterized in that the plugged or crosslinked polymer is water-soluble or hydro-swelling.