ALKALI-SWELLABLE ACRYLIC EMULSIONS COMPRISING ACRYLIC ACID, USE THEREOF IN AQUEOUS FORMULATIONS AND FORMULATIONS CONTAINING SAME

The present invention relates to novel emulsions with alkali swellable thickener, methacrylic acid-free: this monomer previously deemed indispensable in emulsions of this type, which resulted in manufacturers dependent of this raw material. These novel emulsions contain a certain amount of acid 2acrylamido and 2 a-methylpropane sulfonic (or an amps, n° case: 40623 - 75 - 4). They can be manufactured in the absence of surfactant, which prevents the formation of foam.

Finally, they were found to be effective for thickening aqueous media, in particular media whereof the fold is between 5 and 6, such as skin.

Found aqueous formulations optionally containing mineral fillers in very many areas: that of aqueous paints, paper coating slips, suspensions of mineral matter, detergents, cosmetic formulations, or concretes and cements.

Control their rheology is a necessity, both at the point of manufacture, that during their transportation, storage or during their implementation. The diversity of practical constraints at each of these steps returns to a multiplicity of rheological behavior. In the case of a paint for example, one can summarize the need for the skilled person to obtaining a thickening effect thereof, both for reasons of stability over time, that for possible application of paint on a vertical surface, the absence of splash at the time of implementation, or drool after implementation, andc...

In fact, we have designated the products that contribute to the regulation of rheological behavior under the term of thickeners among these thickeners, the skilled person knows long been the particular category alkali-swellable acrylic emulsions, which are polymers emulsified in water from surfactants, polymers being comprised of at least one water-insoluble monomer and at least one water-soluble monomer Ealkali neutralizable with methacrylic acid.

From WO 2011/161508 AC 02802624 2012 - 12 - 13 pct/ib2011/001285 the applicant notes that the expression "direct emulsion of a polymer in water" designates a homogeneous and stable dispersion of polymer particles in water (is not referred herein to emulsions of the oil-in-water or water in oil, which involve the existence of two separate phases, one aqueous and one oily).

The term "alkali-swellable polymer", it means that said polymer is capable, when the medium is alkaline, incorporate an amount of water such that there is formation of a gel.

There are 2 large families of alkali-swellable acrylic thickeners' thickeners ASE (an alkali [...] emulsion or emulsion soluble alkali) and those HASE type ([...] alaising an alkali [...] emulsion or emulsion and hydrophobically modified alkali swellable). The first designate copolymers of methacrylic acid with an ester of this acid is not soluble in water, and the second denote copolymers based on methacrylic acid, an ester of water-insoluble acrylic acid (meth) and a monomer having hydrophobic groups called "associative". These copolymers may be crosslinked further.

The mechanisms of [...] of these products differ. Polymers of the type DNase thicken that neutralized form, resulting in expression of "alkalicarbonates inflatable" " is thus induces a mechanism of ionic repulsion between the different containing carboxylate groups carried by the polymer chain. These ionized groups polarize the molecules of water which causes the increase of the viscosity of the medium. In addition to the above-mentioned ionic phenomenon, the polymers HASE type involve interactions between their associative hydrophobic groups, which contributes also to thicken the medium. These mechanisms, and in particular the character of an alkali swellable emulsions and their ability to thicken an aqueous medium to fold around neutrality, have been described in WO 2007/144721 and "track an associative [...]" (the Proceedings of the Annual Meeting of technique down of tea [...], 2000, 78th, 644702).

There are many applications of these thickeners in the paint, the coating slips, or the cosmetic (see patent applications FR's 2,693 203 AI, FRs 2,872 815 AI, FRs 2,633 930 ai, ai FRs 2,872 815). Further, they are present in commercial form, especially through the ranges of products [...], [...], [...], from WO 2011/161508 AC 02802624 2012 - 12 - 13 pct/ib2011/001285 [...], [...] and [...] marketed by the Company [...] H.S.H..

Returning to the constitution of emulsions ASE and HAse found, methacrylic acid appears today as a monomer conventionally inevitable, which constitutes at least 20% by weight of these thickening polymers. Due to its carboxylic function, it participates in the increase of the viscosity of the medium through a phenomenon ion already described, and it is easily polymerizable aqueous emulsion and in the presence of surfactants with hydrophobic monomers, including associative monomers.

These emulsion polymerizations are widely illustrated in the scientific literature.

We may wish to publication "constraint as year alkalicarbonates [...] emulsion of NDA ITS1 effect pigment is tea spleen d' Polymers in delivering the polyvinyl acetate-butyl acrylate copolymer) a latex film" (Journal Polymers forensic science, hand-: Polymers joining technology, 2005, 43 (22), PPs. 5632 - 5642), "a structural NDA risky properties of the [...] alaising alkalicarbonates dissolvable an emulsion solution" (Journal Polymers forensic science, hand b.: Polymers fuel available, 2002, (18), PPs. 1985 - 1994) "[...] properties of the [...] alaising alkalicarbonates dissolvable an emulsion in-the Salt solution" (Polymers, 1999, 40 (23), PPs. 6369 - 6379), "dissolving into Indonesia waste water require with model waterborne hydrophobic alkalicarbonates [...] emulsion of polymer with branched c20h41 melamines" (Canadian Journal joining technology (1998), 76 (11), PPs. 1779 - 1787), and attempted EP 0,089 213 AIs, the EP 0,646 606 AIs, the EP AI 0,979 833, for the OSD and EP 0,013 836 AIs, from WO 93/2454 AI, U.S. 4268, 641 AIs, U.S. 4421, 902 AIs, U.S. 3,915 921 a1 for HAse found.

Today, methacrylic acid monomer is considered indispensable for the emulsions ASE and HAse found: that is largely integrated into the world industrial and is not reset because by the skilled person. But it is precisely the character [...] methacrylic acid that has a problem. Our indeed an epoch that the shortage of raw material and fluctuation in their cost indexed on that of the barrel of crude oil are a given recurring in the chemical industry; therefore, technology annexed to a raw material exclusively, becomes strategically risky for its manufacturers and users.

From WO 2011/161508 AC 02802624 2012 - 12 - 13 pct/ib2011/001285 i. to eliminate this disadvantage in that the applicant has taken searches for substituting the acrylic acid and methacrylic acid in the emulsions ASE and HAse found. Gold, neither document of the state of the technique does discloses technique for polymerization of acrylic acid emulsion directly, without methacrylic acid and in the presence of a hydrophobic monomer, acrylic acid then represent at least 20% by weight of the monomers to be polymerized.

The applicant has come to demonstrate that such a direct emulsion polymerization has been possible, since is implemented a quantity of a particular monomer which is 2 to-acrylamido 2 a-methylpropane sulfonic (or an amps, n° case: 40623 - 75 - 4). In a manner completely surprising and advantageous, it is thereby possible to make true emulsions ASE HAse found and methacrylic acid-free.

Gold, thickeners based on acrylic acid known to those skilled in the are polymers of acrylic acid crosslinked obtained by precipitation from a solvent (see the document EP is ai 0,584 771), or crosslinked polymers or hydrophobically modified water-in-oil inverse emulsion (see the documents FR's and FR 2,873 126 a1 AI 2,782 086), or finally polymers of high molecular weight (greater than 10,000 000 grams/mole) obtained in solution in water and dried (known as polymers e [...] or SAP; see in particular documents EP is 0,371 421 a1 and US 221,722 ai). Nothing exists in the state of the technique, in order to realize an alkali swellable emulsions, containing at least 20% by weight of acrylic acid and methacrylic acid-free.

In addition, the method object of the present application, has a preferential alternatively which provides other advantages " it can be implemented without surfactant nor solvent other than water. Gold, it is well known that the latter generate many problems in implementing emulsions ASE and HAse found, within an aqueous formulation.

In the case of a paint, there may be creation of inhomogeneities, and even altering properties of the final product [...] to say dry film of paint produced by drying the aqueous formulation. One may also observe the formation of "craters" or in WO 2011/161508 AC 02802624 2012 - 12 - 13 pct/ib2011/001285 insoluble particles which are as many heterogeneities which detracts from the appearance and properties of film surface (mechanical aspect, but also optical properties and surface state). Finally, it is well known that the presence of surfactants in a paint formulation will degrade at final character leachable dry film (see "effect pigment of surfactants in the Poverty liant constraint is les proprietes d' latexes painted", the PROGRESS thein Biologique [...], 2005, 53 (2), PPs. 112 - 118).

Further advantages of the novel emulsions ASE and HAse found without methacrylic acid reside in the fact that they have a dry extract business (greater than 25% by dry weight of active material), are stable in time and characterized by similar particle sizes the emulsions prior; finally, their effectiveness thickening [...].

Another object of the present invention resides in the use of the emulsions mentioned as a thickening agent in aqueous formulations, these being the last object of the present invention.

Also, a first object of the present invention is a method of making direct aqueous emulsion of a polymer, characterized in that said process involves the polymerization reaction, expressed in % by weight of each of the monomers or•) 20% to 80% by weight of acrylic acid, and b) 10% to 90% by weight of at least one acid ester (methacrylic, and c) 0.05% to 22% by weight of acid 2 a-acrylamido 2 a-methylpropane sulfonic, d-) 0 to 1•% by weight of at least one cross-linking monomer, the total has) + d) + d) + and d) being equal to 100%, has) 20% to 80% by weight of acrylic acid, and b) i0% to 90% by weight of at least one ester of (meth) acrylic acid, and c) 10% to 25% by weight of a monomer containing a hydrophobic group, and d) 0.05% to 22% by weight of acid 2 a-acrylamido 2 a-methylpropane sulfonic, or e) 0 to 1% by weight of at least one cross-linking monomer, the total has) + d) + d) +'d) + I) being equal to 1 o0%, from WO 2011/161508 AC 02802624 2012 - 12 - 13 pct/ib2011/001285 other characteristics of this process (temperature, choice of the catalytic system, implementing a transfer agent, use of an optional crosslinker) are those described in the state of the technique, in particular through the documents mentioned to which the skilled person could use.

This method is also characterized in that the ester of the acid (meth) acrylic is selected from ethyl acrylate, butyl acrylate, methyl methacrylate and mixtures thereof.

This method is also characterized in that the hydrophobic group-containing monomer has the general formula•where " n-.

B. r1 r2 Q Male, the n, P and Q are integers and m, the n, P are less than 150, q is greater than 0 and at least one integer of m, n and P is non-zero, R comprises a vinyl polymerizable function, r1 r2 and are identical or different and represent hydrogen atoms or alkyl groups, wherein R ' is a hydrophobic moiety having at least 6 and at most 36 carbon atoms.

This method is also characterized in that the cross-linking monomer is selected from ethylene glycol dimethacrylate, the [...], the diallyl plastiôizer, allyl acrylate, allyl maleates, the methylene-bis-acrylamide, methylene-[...], the [...], the [...], the allyl ethers obtained from polyols.

This method is also characterized in that the aqueous emulsion has between 10% and dry [...] 50% by dry weight of polymer, relative to its total weight.

From WO 2011/161508 AC 02802624,2012 - 12 - 13.7 pct/ib2011/001285 this method is also characterized in that the emulsion has a particle size between 50 nm and 500 nm.

This method is also characterized in that the polymer has a weight average molecular weight of between 20,000 grams/mole/mole and 1,000 000 grams.

In a preferred embodiment, the process does not implement surfactant or a solvent other than water.

Another object of the present invention consists of the use, in a process of making an emulsion ASE or HAse found, acid 2 acrylamido-to-[...] sulfonic, as a complete replacement for the methacrylic acid with acrylic acid.

Another object of the present invention is direct into an aqueous emulsion, a polymer characterized in that it comprises, expressed in % by weight of each of the monomers•has) 20% to 80% by weight of acrylic acid, and b) 10% to 90% by weight of at least one ester of (meth) acrylic acid, and c) 0.05% to 22% by weight of acid 2 a-acrylamido 2 a-methylpropane sulfonic, D.) 0 to 1% by weight of at least one cross-linking monomer, the total has) + d) + d) + and d) being equal to 100%, or has) 20% to 80% by weight of acrylic acid, and b) 10% to 90% by weight of at least one ester of (meth) acrylic acid, •C.) 10% to 25% by weight of a monomer containing a hydrophobic group, d-) 0.05% to 22% by weight of acid 2 a-acrylamido 2 a-methylpropane if!i [...]) 0 to 1% by weight of at least one cross-linking monomer, the total has) + d) + d) +'d) + I) being equal to 100%, from WO 2011/161508 AC/ib2011/001285 02802624 2012 - 12 - 13 pct this emulsion is also characterized in that the hydrophobic group-containing monomer has the general formula•where " the R, r1 r2 Q Male, the n, P and Q are integers and m, the n, P are less than 150, Q is larger than 0 and at least one integer of m, n and P is non-zero, R comprises a vinyl polymerizable function, r1 and r2•are identical or different and represent hydrogen atoms or alkyl groups, wherein R ' is a hydrophobic moiety having at least 6 and at most 36 carbon atoms.

This emulsion is also characterized in that the cross-linking monomer is selected from ethylene glycol dimethacrylate, the [...], the diallyl plastiôizer, allyl acrylate, allyl maleates, the methylene-bis-acrylamide, methylene-[...], the [...], the [...], the allyl ethers obtained from polyols.

This emulsion is also characterized in that it has a dry extract•between 50% and % by dry weight of polymer, relative to its total weight.

This emulsion is also characterized in that it has a particle size between 50 nm and 500 nm.

This emulsion is also characterized in that the polymer has a weight average molecular weight of between 20,000 grams/mole/mole and 1,000 000 grams.

In a preferred embodiment, the emulsion is characterized in that it is free of surfactant ITAC•FS and solvent other than water.

From WO 2011/161508 AC 02802624 2012 - 12 - 13 pct ib2011/001285/another object of the present invention is the use of the emulsion mentioned, as a thickener in an aqueous formulation. Concretely, the emulsion is introduced into the medium to thicken, which will adjust the fold in the vicinity of neutrality, to achieve the desired thickening effect. Those skilled in the, from routine experiments, may find the crease from which one observes the burring.

This use is also characterized in that said formulation is selected from a•aqueous paint, a paper coating slip, an aqueous suspension of mineral matter, a detergent, a cosmetic formulation, or containing a hydraulic binder, and finally a cosmetic formulation, more particularly a cosmetic formulation for application to the skin or a body region andits fold is between 5 and 6.

A final object of the present invention resides in an aqueous formulation containing the emulsion mentioned, said formulation is chosen from aqueous paint, a paper coating slip, an aqueous suspension of mineral matter, a detergent, a cosmetic formulation, or containing a hydraulic binder, a cosmetic formulation for application to the skin or a body region having the fold is between 5 and 6.

From WO 2011/161508 AC 02802624 2012 - 12 - 13 pct ib2011/001285 examples example 1/test no. 1 according to the invention this test relates to the manufacture of an emulsion ASE, containing a copolymer consisting of, expressed in % by weight of each of its monomers•has) 36.4% acrylic acid, and b) 62.4% of ethyl acrylate, and c) 1.2% AMPS in a 1 liter reactor equipped with a mechanical stirrer and a heating oil bath type, 550 g of water is introduced [...] and 7.0 g of a solution of amps (solution at 55% in water AMPS neutralized by sodium hydroxide, sold by [...] as an amps 2405).

The medium is heated to 78 °c is then introduced through a funnel the catalytic system consisting of 0.96 g of ammonium persulfate dissolved in 10 g of water and [...] 0,096 g of sodium metabisulfite dissolved in 10 g of water [...].

Is then introduced, continuously and progressively 236 g of ethyl acrylate and 85 g of acrylic acid (to 90%).

For the duration of the addition, the temperature of the reaction medium is maintained at 78 °c (± 2).

Once the addition is completed, the pump is rinsed with 20 g of water [...] and then allowed to react for 30 minutes at 78 °c (± 2).

Then added 0.10 g of ammonium persulfate dissolved in 25 g of water in 30 minutes while maintaining the temperature at 80 °c (+ 2) and allowed to react for 1 hour to 87 °c (± 2).

From WO 2011/161508 AC 02802624 2012 - 12 - 13 1i PTC/ib2011/001285 the resulting emulsion containing 32.4% by dry weight of active material, and having a particle size, measured by dynamic light scattering is equal to 99 nm.

Comparative tests which was initially sought to make the same polymer as in experiment 1, but without implementing AMPS, namely a polymer consisting of 36.5% by weight of acrylic acid and 63.5% by weight of ethyl acrylate.

For this purpose, there are provided the same protocol as above, except for the initial introduction of amps. React to 87 °c during 1 hour, observed the formation of a precipitate disorder in solution, a portion of which is fixed at the axis of the reactor (riprap). The size of the formed particles is greater than 500 nm. The medium, very inhomogeneous and rich in larger particles, is not amenable to manipulations, and in particular to pumping operations. The storage of more than lead to sedimentation of the product.

Was then implemented an amount of amps greater than 22% by weight of the total mass of the monomers engaged, by a procedure which is identical to said described in experiment no. 1, the copolymer is then formed, expressed as % by weight of each monomer thereof:

a) 36.5% acrylic acid, and b) 38.5% of ethyl acrylate, and c) 25.0% AMPS.

Then observed the formation of insoluble species that precipitate in the medium.

Was then replaced the I ' an amps (1.2%, weight for weight) by another monomer implemented in the emulsions ase and HAse found,: ethyl acrylate. Is not achieved making emulsions homogeneous; the observations are the same as previously, with the formation of a precipitate, the phenomenon of riprap, and the adverse consequences which it makes.

From WO 2011/161508 AC 02802624 2012 - 12 - 13 pct/ib2011/001285 was then substituted the I ' an amps (always 1.2% by-weight) by styrene, lauryl methacrylate, 2 a-sulfoethyl methacrylate, styrene sulfonate, the sodium salt of the 1 a-allyloxy 2 a-hydroxy propyl sulphonate ([...] cop 1) for identical results (presence of insoluble, and riprap phenomenon).

Test no. 2 to 11 according to the invention those tests no. 2 to 11 relate to the synthesis of other emulsions illustrating the invention, according to the same procedure described above.

The tests no. 2 to 8 illustrate other compositions monomeric with a mass fraction of AMPS attached to 1.2%, while the tests no. 9 to 11 illustrate other rate in an amps (was then held the constant the mass ratio between ethyl acrylate and acrylic acid).

The characteristics of emulsions obtained are given in table 1.

Test n° monomer composition (mass %) 1, 1.2 an amps/62.4 ae/36.4 A.A 2, 1.2 an amps/3, 1.2 an amps/74.6 68.7 ae/30.1 AAs. Ae] 24.2 AAs 4, 1.2 1.2 an amps/80.4 .ae/18.4 AAs an amps/28.35 ABUs 70.45 AAs an amps/6, 1.2 an amps/MMA 74.1 ae/18.4 aa/6.3/7, 1.2 1.2 67.8 ae/18.4 aa/12.6 MMA/ae/35, 8 an amps/53.25 A.A AE 32.4 32.8 29.6 32.2 37.6 33.2 32.4 diameter particle (a.m.) 8, 9.75 methc22oe25 33.1 185, 9 10 an amps/57.9 ae/32.1 an amps/55.4 ae/29.6 29.6 175, 15 AAs A.A 29.6 215, 11 20 an amps/52.9 ae/27.1 AAs 29.6 276 table 1 this table, methc22oe25 denotes a monomer of formula (I-) wherein R denotes the function methacrylate, m=p=0, n=25, andR ' denotes a methyl group, from WO 2011/161508 AC/EC 02802624 2012 - 12 - 13 pct ib2011/001285 denotes ethyl acrylate, butyl acrylate ABUs, WADA methyl methacrylate, AA and WADA acrylic and methacrylic acids.

Example 2 this example illustrates the thickening power of said emulsions, implementations in water to have an active material content of 5% in dry polymer.

•after introduction into water, the medium is neutralized by the addition of soda to a fold between 4.9 and 5.5 and measurement of the viscosity [...][...], 25 °c to 100 revolutions/min and, whose values are reported in table 2 the emulsion test n° viscosity (mPas) [...] the gel to 5% table 2 this shows the character thickening emulsions produced, from the instant at which they are placed under alkaline conditions.

Furthermore, it is surprising to note that the thickening effect is manifested for a bend as low; usually, the emulsions ASE and HAse found thicken in fold area between 6 and 7.

This thickening to "bottom fold" is particularly difficult to achieve, and is quite interesting in the cosmetic field, where the thickening effect is searched to a fold adjacent the skin, [...] to say in a zone comprised between 5 and 6 units fold. It is reported in the document EP-ai 2,027 169.

From WO 2011/161508 AC 02802624 2012 - 12 - 13 pct/ib2011/001285 example 3 this example illustrates the implementation, in the formulation of a concrete, emulsions commercial ASE thickener (surfactant-containing) and of an emulsion according to the invention free of surfactant.

For this purpose, are made a concrete according to methods well described in the literature, consisting of:

300 kg cement EMC 1, 52, 5 n-; 880 of pebble 10/20; kg of sand 0/4; whose water cement ratio e/c is set to 0.5, and wherein is introduced, based on the dry weight of cement:

- 1.23% by weight in the state of a dispersant sold by [...] as [...] 1030; - 1% by weight in the state of an antifoam agent sold by [...] as FEP [...] 7169.

The assays, and b, c and d, respectively involve embodied in the formulation of 0.7% by weight of concrete in the state:

- an emulsion ASE surfactant-containing and marketed by the Company under the name [...][...] 730; - an emulsion ASE surfactant-containing and marketed by the Company under the name [...][...] 35; - an emulsion HASE type surfactant-containing and marketed by the Company under the name [...][...] 66; - an emulsion according to the invention, which is described in experiment no. 1.

For each of the assays, and b, c and d, was measured air occluded, according to EN 123507. Obtained respectively 9.5%, 12.0%, 12.5% and 3.0%.

The thickening emulsion according to the invention results in reduced very substantially the amount of air introduced in the formulation. Are thus ultimately a more compact, to the improved resistance.

FROM WO 2011/161508 AC/IB2011/001285 02802624 2012 - 12 - 13 PCT