Thickening cyclo-alkylated urethane copolymer

Abstract

The invention relates to a thickening urethane copolymer prepared by means of cyclohexanol substituted by a linear or branched C4-C24-alkyl group or by a linear or branched C4-C24-alkylene group. The invention also relates to the process for preparing said copolymer and to the use thereof in aqueous compositions, in particular in coating compositions.

Description

[0001] CYCLOALKYLATED URETHANE COPOLYMER THICKENER

[0002] The invention relates to a thickening urethane copolymer prepared using cyclohexanol substituted by a linear or branched C4-C24-alkyl group or by a linear or branched C4-C24-alkylene group. The method of preparing this copolymer and its use in aqueous compositions, in particular in coating compositions, are also part of the invention.

[0003] Many technical fields require the use of aqueous compositions. In particular, aqueous hydraulic binder compositions, aqueous adhesive compositions, aqueous detergent compositions, aqueous cosmetic compositions, aqueous ink compositions, aqueous paper coating compositions, aqueous coating compositions, in particular aqueous varnish compositions or aqueous paint compositions, for example aqueous decorative paint compositions or aqueous industrial paint compositions, are known. In addition to their functional properties, these aqueous compositions must have a texture suitable for their use or storage. In particular, they must have a suitable viscosity. In addition, these aqueous compositions must be able to be used under conditions that can vary widely. In particular, the viscosity of these aqueous compositions may vary or degrade.

[0004] The functional properties of these aqueous compositions may therefore be impaired if their rheological behavior is not suitable, for example to prevent sedimentation or phase separation phenomena during storage time, which may also manifest themselves by viscosity variations. Such variations or degradations are particularly detrimental or damaging for aqueous hydraulic binder compositions, for aqueous adhesive compositions, for aqueous detergent compositions, for aqueous cosmetic compositions, for aqueous ink compositions, for aqueous paper coating compositions, for aqueous coating compositions, in particular for aqueous varnish or paint compositions. There is therefore a need to be able to have aqueous compositions which do not have such drawbacks or aqueous compositions which do not lead to such problems.

[0005] In particular, it is particularly useful to be able to have available aqueous coating compositions, in particular aqueous varnish or paint compositions, whose viscosity is adapted to allow the maintenance of their homogeneity as well as the integrity of their functional properties. Maintaining the viscosity and limiting the loss of viscosity of these aqueous compositions should be possible for wide ranges of shear rates.

[0006] Therefore, many aqueous coating compositions use rheology-modifying polymers. These polymers should make it possible to give aqueous compositions the desired rheological properties for wide shear rate ranges. These polymers should also improve the shear-thinning of these aqueous compositions by giving them sufficient pseudo-plasticity, ensuring their stability and homogeneity during their storage life, facilitating their transfer to application tools and helping to limit the appearance of drips once applied. The compatibility of the different constituents of an aqueous coating composition must also be taken into account. In particular, it is important that the thickening copolymer and the pigments and binders used have good compatibility.

[0007] Furthermore, it is also important to improve the pigment compatibility of aqueous coating compositions, especially paint compositions, and particularly with regard to the addition of pigment concentrates used for coloring. Without good pigment compatibility, the rheology of the composition can be significantly degraded. Insufficient pigment compatibility can also lead to a reduction in coloring strength and result in an uneven or washed-out shade, which may result in the use of a higher quantity of pigment or the presence of aesthetic defects in the final coating.

[0008] WO 2012172249 and WO 2013072592 describe paint formulations thickened using a non-ionic associative polymer comprising alkyl groups derived from 4-alkyl-cyclohexylols. WO 2020084200 describes the preparation of urethane polymers by reactive extrusion. Polymers known as thickening agents do not always provide a satisfactory solution to these various problems. There is therefore a need for improved rheology-modifying copolymers. The copolymer according to the invention makes it possible to provide a solution to all or part of the problems of the polymers of the prior art.

[0009] Thus, the invention provides a copolymer P prepared by at least one polymerization reaction:

[0010] • at least one isocyanate compound (a) independently chosen from a diisocyanate compound (a1), a polyisocyanate compound (a2) and combinations thereof;

[0011] • at least one polyhydroxylated compound (b);

[0012] • at least one compound (c) of formula I:

[0013] R-CôHie-Qm-OH in which:

[0014] - R independently represents a group in position 3 of the cycle and chosen from a linear C4-C24-alkyl group, a branched C4-C24-alkyl group, a linear C4-C24-alkylene group, a branched C4-C24-alkylene group and combinations thereof;

[0015] - m independently represents 0 or a number from 1 to 100;

[0016] - Q represents a group chosen from an oxyethylene group, an oxypropylene group, an oxybutylene group and their combinations.

[0017] Preferably for the copolymer P according to the invention, the isocyanate compound (a) is a diisocyanate compound (a1) chosen from:

[0018] - symmetrical aromatic diisocyanate compounds, preferably:

[0019] 2,2'-diphenylmethylene diisocyanate (2,2'-MDI) and 4,4'-diphenylmethylene diisocyanate (4,4'-MDI);

[0020] 4,4'-dibenzyl diisocyanate (4,4'-DBDI);

[0021] toluene 2,6-diisocyanate (2,6-TDI); m-xylylene diisocyanate (m-XDI);

[0022] - symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (H12MDI);

[0023] - symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI); - unsymmetrical aromatic diisocyanate compounds, preferably:

[0024] 2,4'-diphenylmethylene diisocyanate (2,4'-MDI);

[0025] 2,4'-dibenzyl diisocyanate (2,4'-DBDI);

[0026] 2,4-toluene diisocyanate (2,4-TDI); unsymmetrical alicyclic diisocyanate compounds, preferably isophorone diisocyanate (IPDI).

[0027] More preferably according to the invention, the compound (al) is chosen from IPDI, HDI, H12MDI and their combinations.

[0028] Also preferably for the copolymer P according to the invention, the isocyanate compound (a) may be a polyisocyanate compound (a2) strictly comprising more than 2 isocyanate functions or more than 2.2 isocyanate functions or even more than 2.5 isocyanate functions. More preferably, the polyisocyanate compound (a2) comprises more than 2.6 isocyanate functions or more than 2.7 isocyanate functions or more than 3 isocyanate functions. Also more preferably, the polyisocyanate compound (a2) comprises from 2.2 to 6 isocyanate functions, from 2.2 to 4 isocyanate functions, from 2.2 to 3.5 isocyanate functions, from 2.5 to 6 isocyanate functions, from 2.2 to 5 isocyanate functions, from 2.5 to 4 isocyanate functions, from 2.5 to 3.5 isocyanate functions, in particular from 2.6 to 3.3 isocyanate functions.

[0029] Also preferably, the polyisocyanate compound (a2) is chosen from: triphenylmethane-4,4',4”-triisocyanate or 1,1',1”-methylidynetris (4-isocyanatobenzene);

[0030] - an isocyanurate compound, in particular an isocyanurate compound of a compound chosen from:

[0031] ■ symmetrical aromatic diisocyanate compounds, preferably: 2,2'-diphenylmethylene diisocyanate (2,2'-MDI) and 4,4'-diphenylmethylene diisocyanate (4,4'-MDI);

[0032] 4,4'-dibenzyl diisocyanate (4,4'-DBDI);

[0033] toluene 2,6-diisocyanate (2,6-TDI); m-xylylene diisocyanate (m-XDI);

[0034] ■ symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (H12MDI); ■ symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI);

[0035] ■ unsymmetrical aromatic diisocyanate compounds, preferably: 2,4'-diphenylmethylene diisocyanate (2,4'-MDI);

[0036] 2,4'-dibenzyl diisocyanate (2,4'-DBDI);

[0037] toluene 2,4-diisocyanate (2,4-TDI);

[0038] - a trimeric biurea compound, in particular a trimeric biurea compound of a compound chosen from:

[0039] ■ symmetrical aromatic diisocyanate compounds, preferably: 2,2'-diphenylmethylene diisocyanate (2,2'-MDI) and 4,4'-diphenylmethylene diisocyanate (4,4'-MDI);

[0040] 4,4'-dibenzyl diisocyanate (4,4'-DBDI);

[0041] toluene 2,6-diisocyanate (2,6-TDI); m-xylylene diisocyanate (m-XDI);

[0042] ■ symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (H12MDI);

[0043] ■ symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI);

[0044] ■ unsymmetrical aromatic diisocyanate compounds, preferably: 2,4'-diphenylmethylene diisocyanate (2,4'-MDI);

[0045] 2,4'-dibenzyl diisocyanate (2,4'-DBDI);

[0046] toluene 2,4-diisocyanate (2,4-TDI);

[0047] ■ asymmetric alicyclic diisocyanate compounds, preferably isophorone diisocyanate (IPDI).

[0048] More preferably, compound (a2) is selected from triphenylmethane-4,4',4”- triisocyanate, l,l',l”-methylidynetris (4-isocyanatobenzene), HDI isocyanurate, IPDI isocyanurate, PDI isocyanurate, HDI biurea trimer and IPDI biurea trimer, PDI biurea trimer.

[0049] According to the invention, the polyisocyanate compound (a2) is different from the diisocyanate compound (a1).

[0050] Preferably for the copolymer P according to the invention, the polyhydroxylated compound (b) is a compound (bl) of formula II: HO-U-OH

[0051] (II) in which:

[0052] - L independently represents an oxyalkylene residue;

[0053] - n independently represents a number ranging from 30 to 1000.

[0054] Preferably for the copolymer P according to the invention, the polyhydroxylated compound (b) is a compound (bl) of formula II in which:

[0055] - L independently represents an oxyethylene residue; or

[0056] - n independently represents a number ranging from 50 to 400, preferably from 100 to 300. More preferably for the copolymer P according to the invention, the polyhydroxylated compound (b) is a compound (bl) of formula II in which L independently represents an oxyethylene residue and p independently represents a number ranging from 50 to 400, preferably from 100 to 300.

[0057] According to the invention, the compound (b1) of formula II may be combined with a non-alkoxylated compound (b2) comprising at least three hydroxyl groups. Preferably according to the invention, the compound (b2) comprises three hydroxyl groups. Much more preferably, it is chosen from glycerol, pentaerythritol and their combinations.

[0058] According to the invention, the polyhydroxylated compound (b) may also be polyethoxylated pentaerythritol or a polyalkoxylated compound (b3) comprising at least three hydroxyl groups. Preferably according to the invention, the compound (b3) is different from the compound (b2) and comprises three hydroxyl groups. Much more preferably,

[0059] 11 is polyethoxylated glycerol.

[0060] Advantageously according to the invention, the copolymer P can be prepared using one or more combinations of compounds (b1), (b2) and (b3).

[0061] Preferably according to the invention, compounds (b), (bl) or (b3) independently have a molar mass (Mw) measured by CES ranging from 1,500 to 40,000 g / mol, preferably from 2,000 to 20,000 g / mol, more preferably from 2,000 to 15,000 g / mol or from 2,000 to

[0062] 12,000 g / mol.

[0063] According to the invention, the molar mass of compounds (b), (bl) or (b3) is determined by Size Exclusion Chromatography (SEC) or in English "Gel Permeation Chromatography" (GPC). This technique uses a "Waters" brand liquid chromatography apparatus equipped with a detector. This detector is a "Waters" 2414 type refractometric concentration detector. This liquid chromatography apparatus is equipped with two size exclusion columns in order to separate the different molecular weights of the polymers or compounds studied. The liquid elution phase is an organic phase composed of THF (HPLC grade, non-stabilized). In a first step, approximately 25 mg of compound is solubilized in 5 mL of THF, to which 0.1 mol% of water used as an internal flow marker is added. Then, the solution is filtered at 0.2 μm. 50 pL are then injected into the chromatography device (eluent: THF, HPLC grade, non-stabilized).The liquid chromatography apparatus contains an isocratic pump (“Waters” 515) with a flow rate set at 0.3 mL / min. The chromatography apparatus also includes an oven which includes a column system in series: an “Agilent” PLgel MiniMIX-A type column of 250 mm length and 4.6 mm diameter followed by an “Agilent” PLgel MiniMIX-B type column of 250 mm length and 4.6 mm diameter. The detection system consists of a refractometric detector of the RI “Waters” 2414 type. The columns are maintained at a temperature of 35 °C and the refractometer is brought to a temperature of 35 °C. The chromatography apparatus is calibrated using polymethyl methacrylate standards certified by the supplier “Agilent” (“EasiVial” PMMA).

[0064] Preferably according to the invention, compound (c) is a compound of formula I in which R independently represents a group chosen from a linear C4-C24-alkyl group or a linear C4-C24-alkylene group, preferably a linear C6-C20-alkyl group or a linear C6-C20-alkylene group, more preferably a linear C12-C18-alkyl group or a linear C12-C18-alkylene group, much more preferably a linear Cis-alkyl group.

[0065] According to the invention, the alkylene groups may comprise from 1 to 6 unsaturations, preferably 1, 2 or 3 unsaturations. The preferred alkylene group comprises a single unsaturation, preferably a terminal unsaturation. Indeed, the unsaturations of the alkylene groups may be terminal or be present within the alkylene chain.

[0066] Preferably according to the invention, compound (c) is a compound of formula I in which m independently represents 0 or a number ranging from 2 to 50 or from 2 to 20 or from 2 to 10. Preferably according to the invention, compound (c) is a compound of formula I in which Q represents an oxyethylene group or a combination of oxyethylene groups and oxypropylene groups, preferably in a molar proportion (oxyethylene groups / oxypropylene groups) ranging from 95 / 5 to 50 / 50, preferably ranging from 80 / 50 to 70 / 30 or from 65 / 35 to 55 / 45.

[0067] More preferably according to the invention, compound (c) is a compound of formula I in which:

[0068] - R independently represents a group chosen from a linear C4-C24-alkyl group or a linear C4-C24-alkylene group, preferably a linear C6-C20-alkyl group or a linear C6-C20-alkylene group, more preferably a linear C12-C18-alkyl group or a linear C12-C18-alkylene group, much more preferably a linear C18-alkyl group,

[0069] - m independently represents 0 or a number from 2 to 50 or from 2 to 20 or from 2 to 10; and

[0070] - Q represents an oxyethylene group or a combination of oxyethylene groups and oxypropylene groups, preferably in a molar proportion (oxyethylene groups / oxypropylene groups) ranging from 95 / 5 to 50 / 50, preferably ranging from 80 / 50 to 70 / 30 or from 65 / 35 to 55 / 45.

[0071] Much more preferably according to the invention, compound (c) is a compound of formula I in which:

[0072] - R independently represents a group chosen from a linear C4-C24-alkyl group, preferably a linear C6-C20-alkyl group, more preferably a linear C12-C18-alkyl group, much more preferably a linear C15-alkyl group,

[0073] - m independently represents 0 or a number from 2 to 50 or from 2 to 20 or from 2 to 10; and

[0074] - Q represents an oxyethylene group or a combination of oxyethylene groups and oxypropylene groups, preferably in a molar proportion (oxyethylene groups / oxypropylene groups) ranging from 95 / 5 to 50 / 50, preferably ranging from 80 / 50 to 70 / 30 or from 65 / 35 to 55 / 45. Preferably according to the invention, compound (c) is a compound of formula I in which R independently represents a linear alkyl group.

[0075] Compound (c) according to the invention is a compound of formula I which comprises a CÔHIO group comprising 6 carbon atoms and which is cyclic.

[0076] For the preparation of the copolymer P according to the invention, the quantities of compounds (a), (b) and (c) can vary. Preferably for the copolymer P, the polymerization reaction involves:

[0077] - from 10 to 79.9 mol% or from 10 to 74.5 mol%, preferably from 10 to 68 mol% or from 10 to 60 mol%, of monomer (a) or

[0078] - from 20 to 89.9 mol% or from 25 to 89.5 mol%, preferably from 30 to 88 mol% or from 35 to 85 mol%, of monomer (b), or

[0079] - from 0.1 to 70 mol% or from 0.5 to 65 mol%, preferably from 2 to 60 mol% or from 5 to 55 mol%, of monomer (c), relative to the total molar quantity of monomers (a), (b) and (c).

[0080] Much more preferably according to the invention, the polymerization reaction can implement:

[0081] - from 10 to 79.9 mol% or from 10 to 74.5 mol% of monomer (a),

[0082] - from 20 to 89.9 mol% or from 25 to 89.5 mol% of monomer (b), and

[0083] - from 0.1 to 70 mol% or from 0.5 to 65 mol% of monomer (c), relative to the total molar quantity of monomers (a), (b) and (c).

[0084] Even more preferably according to the invention, the polymerization reaction can implement:

[0085] - from 10 to 68 mol% or from 10 to 60 mol% of monomer (a),

[0086] - from 30 to 88 mol% or from 35 to 85 mol% of monomer (b), and

[0087] - from 2 to 60 mol% or from 5 to 55 mol% of monomer (c), relative to the total molar quantity of monomers (a), (b) and (c).

[0088] According to the invention, the polymerization reaction can use only compounds (a), (b) and (c) or use one or more other additional compounds. Then, the polymerization reaction can also use at least one hydrophobic compound (d) different from compound (c), preferably chosen from a compound of formula (III):

[0089] R^OE) q OP) r -OH in which:

[0090] - q and r, identical or different, independently represent 0 or an integer or decimal number less than 150, in particular q or r is different from 0,

[0091] - OE independently represents a CH2CH2O group,

[0092] - OP independently represents a group chosen from CH(CH3)CH2O and CH2CH(CH3)O,

[0093] - R 1independently represents a linear or branched C4-C40-alkyl group, preferably a linear or branched C6-C60-alkyl group, more preferably a linear or branched C6-C22-alkyl group.

[0094] Preferably, the polymerization reaction may involve less than 60 mol%, preferably from 0.05 to 60 mol%, in particular from 0.1 to 60 mol%, more preferably less than 50 mol%, preferably from 0.05 to 50 mol%, in particular from 0.1 to 50 mol%, of compound (d) relative to the total molar quantity of compounds involved.

[0095] The copolymer P according to the invention can be used in many technical fields, in particular as a rheology control agent. It can be incorporated into different compositions. Thus, the invention provides a rheological control composition comprising at least one copolymer P according to the invention. The rheological control composition according to the invention can be treated in an acidic manner leading to a pH of less than 8, preferably to a pH of greater than 6. This treatment can be carried out using an acid, in particular a carboxylic acid such as acetic acid or lactic acid.

[0096] The rheological control composition according to the invention may also comprise at least one solvent, in particular water or a coalescence solvent, for example glycol, butyl glycol, butyl diglycol, monopropylene glycol, ethylene glycol, ethylene diglycol, “Dowanol” products with CAS number 34590-94-8), “Texanol” products with CAS number 25265-77-4); or combined with at least one additive chosen from an amphiphilic compound, in particular a surfactant compound, preferably a hydroxylated surfactant compound, for example alkyl-polyalkylene glycol, in particular alkyl-polyethylene glycol and alkyl-polypropylene glycol; a polysaccharide derivative, for example cyclodextrin, cyclodextrin derivative, polyethers, alkyl-glucosides; a hydrotropic compound, an antifoaming agent, a biocidal agent and combinations thereof.

[0097] The rheological control composition according to the invention is particularly suitable for facilitating the implementation of pigments in aqueous medium, in particular organic or mineral pigments. It can be incorporated into a particular pigmented formulation. Thus, the invention provides an aqueous formulation comprising:

[0098] - at least one rheological control composition according to the invention; optionally

[0099] - at least one organic or mineral pigment or organic, organo-metallic or mineral particles, for example calcium carbonate, talc, kaolin, mica, silicates, silica, metal oxides, in particular titanium dioxide, iron oxides; and optionally

[0100] - at least one agent selected from a particle spacing agent, a dispersing agent, a steric stabilizing agent, an electrostatic stabilizing agent, an opacifying agent, a coloring agent, a solvent, a coalescing agent, an anti-foaming agent, a preservative, a biocidal agent, a spreading agent, a thickening agent, a film-forming copolymer and mixtures thereof.

[0101] Preferably, the formulation according to the invention is a coating formulation, in particular an ink formulation, a varnish formulation, an adhesive formulation, a paint formulation, for example decorative paint or industrial paint.

[0102] The copolymer P according to the invention can also be used in the field of printing, in particular textile printing. Thus, the invention provides a concentrated aqueous pigment paste comprising at least one copolymer P according to the invention and at least one organic or mineral colored pigment.

[0103] The invention also provides a method for controlling the viscosity of an aqueous composition which comprises the addition of at least one copolymer P according to the invention to this composition. The method for controlling the viscosity according to the invention is implemented for an aqueous composition which is an aqueous formulation according to the invention.

[0104] The advantageous, particular or preferred characteristics of the copolymer P according to the invention define rheological control compositions, aqueous formulations, pigment pastes as well as viscosity control methods according to the invention which are also advantageous, particular or preferred.

[0105] The following examples illustrate the various aspects of the invention.

[0106] Examples:

[0107] Example 1: Preparation of copolymers P according to the invention:

[0108] PI copolymer according to the invention:

[0109] In a 2 L glass reactor equipped with mechanical stirring, a vacuum pump, a nitrogen inlet and heated by means of a double jacket in which oil circulates, a compound (b) (polyethylene glycol - molecular mass 10000 g / mol) (154.5 g) is introduced and heated to 95°C under vacuum. Then, under stirring and in an inert atmosphere, 0.33 g of a DBU catalyst (1,8-diazabicyclo[5.4.0]undec-7-ene) is added to the medium and then a compound (cl) (hydrogenated cardanol, of formula I in which R represents a linear Cis-alkyl group and m represents 0) (7.7 g) and dodecan-1-ol (4.6 g) are added over 10 min. Then, a diisocyanate compound (al) (isophorone diisocyanate, IPDI) (11 g) is introduced by means of a syringe and stirred at 150 rpm. The reaction is continued at 100°C for 1 hour.

[0110] Then, we check that the isocyanate level is zero by a back titration. We take 1 g of the reaction medium to which we add an excess of dibutylamine (1 molar for example) which reacts with the isocyanate functions potentially present in the medium. Any unreacted dibutylamine is then titrated with hydrochloric acid (1 N for example). We can then deduce the quantity of isocyanate functions present in the reaction medium. If this is not zero, the reaction is extended by periods of 15 minutes until the reaction is complete. The resulting PI copolymer is formulated using ethoxylated alcohol surfactant compounds (“Emulan” HE 51 “Basf”) (48.3 g) and (“Simulsol” 0x1008 “Seppic”) (48.3 g), 1000 ppm of a biocidal agent (“Biopol” SMV “Chemipol”), 1000 ppm of an antifoam agent (“Tego” 1488 “Evonik”) and water (725 g).An aqueous rheological control composition is obtained consisting of 17.5% by mass of PI copolymer according to the invention, 9.5% by mass of surfactant compounds and 73% by mass of water.

[0111] Copolymer P2 according to the invention: In a 2 L glass reactor equipped with mechanical stirring, a vacuum pump, a nitrogen inlet and heated by means of a double jacket in which oil circulates, a compound (b) (polyethylene glycol - molecular mass 10,000 g / mol) (151.5 g) is introduced and heated to 95°C under vacuum. Then, under stirring and in an inert atmosphere, 0.33 g of a DBU catalyst is added to the medium and then a compound (cl) (hydrogenated cardanol) (7.7 g), dodecanol (3.4 g) and octan-l-ol (0.6 g) are added over 15 min. Then, a diisocyanate compound (al) (isophorone diisocyanate, IPDI) (10.8 g) is introduced by means of a syringe and under stirring at 150 rpm. The reaction is continued at 100°C for 1 hour.

[0112] Then, the isocyanate level is checked to be zero by back-dosing. The copolymer P2 obtained is formulated using ethoxylated alcohol surfactant compounds (“Emulan” HE 51 “Basf”) (48.3 g) and (Simulsol 0x1008 “Seppic”) (48.3 g), 1000 ppm of a biocidal agent (“Biopol” SMV “Chemipol”), 1000 ppm of an anti-foaming agent (“Tego” 1488 “Evonik”) and water (725 g). An aqueous rheological control composition is obtained consisting of 17.5% by mass of copolymer P2 according to the invention, 9.5% by mass of surfactant compounds and 73% by mass of water.

[0113] Examples 2: preparation and characterization of an aqueous paint formulation according to the invention:

[0114] By mixing the different ingredients under agitation, a Fl matt paint formulation according to the invention is prepared. The compounds and quantities (g) used are detailed in Table 1.

[0115] Table 1 Then, the paint formulation Fl is colored by adding 5% by weight of a black pigment (“Colanyl” N500 black “Clariant”) to obtain the colored formulation Fl according to the invention.

[0116] Then, for the colored Fl formulation, we measure, at 25°C: the Brookfield viscosity at 10 rpm (pBlO, mPa.s); the Brookfield viscosity at 100 rpm (pBlOO, mPa.s); the Cone Plan viscosity or ICI viscosity measured at high speed gradient (pi, mPa.s); the Stormer viscosity measured using the standard module, at medium speed gradient (pS, Krebs Units or KU).

[0117] The results are measured immediately after the addition of the black pigment (T=0) and measured 24 hours after this addition (T=24H). They are presented in Table 2.

[0118] The pigment compatibility of the Fl formulation is evaluated on a dry film of paint. The test, known as such, of rubbing out the colored paint applied with a finger at a wet thickness of 150 micrometers on a contrast card (rub out test) makes it possible to subject a small part of the surface of the freshly applied colored paint film to a shearing effect generated by a circular movement of the finger. The shearing effect can modify the stability and distribution of the colored pigment in the matrix that constitutes the colored paint film and consequently, the intensity of the coloring at the location of the sheared area.

[0119] Once the colored paint film is dry, the difference in coloring between the initially sheared area of ​​the colored paint film and the unsheared area of ​​colored paint is measured using a spectro-guide sphere gloss type spectrophotometer marketed by the company "Byk".

[0120] The color difference is quantified by the AE value calculated from the measurement parameters corresponding to the known L*a*b* color space. A low AE value means a reduced color difference between the sheared and unsheared areas, and therefore an improvement in pigment compatibility.

[0121] The unsheared colored paint area is also subject to a measurement corresponding to one of the parameters of the L*a*b* color space. The L* parameter quantifies the intensity of the coloring. A low value for the L* parameter means reduced lightness and therefore a greater black intensity corresponding to an improvement in the pigment compatibility of the evaluated paint formulation in which the copolymer according to the invention is implemented. The results are presented in the table

[0122] 2. For the colored Fl formulation according to the invention, the copolymer according to the invention allows good control of the different components of the viscosity, both after preparation and over time. The copolymer according to the invention provides good pigment compatibility to this paint formulation.

Claims

CLAIMS 1. Copolymer P prepared by at least one polymerization reaction: • at least one isocyanate compound (a) independently chosen from a diisocyanate compound (a1), a polyisocyanate compound (a2) and combinations thereof; • at least one polyhydroxylated compound (b); • at least one compound (c) of formula I: R-CôHw-Qm-OH in which: - R independently represents a group in position 3 of the cycle and chosen from a linear C4-C24-alkyl group, a branched C4-C24-alkyl group, a linear C4-C24-alkylene group, a branched C4-C24-alkylene group and combinations thereof; - m independently represents 0 or a number from 1 to 100; - Q represents a group chosen from an oxyethylene group, an oxypropylene group, an oxybutylene group and their combinations.

2. Copolymer P according to claim 1 for which the isocyanate compound (a) is: • a diisocyanate compound (al) chosen from: symmetrical aromatic diisocyanate compounds, preferably: 2,2'-diphenylmethylene diisocyanate (2,2'-MDI) and 4,4'-diphenylmethylene diisocyanate (4,4'-MDI); 4,4'-dibenzyl diisocyanate (4,4'-DBDI); toluene 2,6-diisocyanate (2,6-TDI); m-xylylene diisocyanate (m-XDI); - symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (H12MDI); - symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI); - asymmetric aromatic diisocyanate compounds, preferably: 2,4'-diphenylmethylene diisocyanate (2,4'-MDI); 2,4'-dibenzyl diisocyanate (2,4'-DBDI); toluene 2,4-diisocyanate (2,4-TDI); - asymmetric alicyclic diisocyanate compounds, preferably isophorone diisocyanate (IPDI), more preferably, compound (al) is chosen from IPDI, HDI, H12MDI and combinations thereof; or • a polyisocyanate compound (a2) comprising strictly more than 2 isocyanate functions or more than 2.2 isocyanate functions or even more than 2.5 isocyanate functions; preferably, the polyisocyanate compound (a2) comprises more than 2.6 isocyanate functions or more than 2.7 isocyanate functions or more than 3 isocyanate functions; more preferably, the polyisocyanate compound (a2) comprises from 2.2 to 6 isocyanate functions, from 2.2 to 4 isocyanate functions, from 2.2 to 3.5 isocyanate functions, from 2.5 to 6 isocyanate functions, from 2.2 to 5 isocyanate functions, from 2.5 to 4 isocyanate functions, from 2.5 to 3.5 isocyanate functions, in particular from 2.6 to 3.3 isocyanate functions; or a polyisocyanate compound (a2) chosen from: triphenylmethane-4,4',4”-triisocyanate or 1,1',1”-methylidynetris (4-isocyanatobenzene); - an isocyanurate compound, in particular an isocyanurate compound of a compound chosen from: ■ symmetrical aromatic diisocyanate compounds, preferably: 2,2'-diphenylmethylene diisocyanate (2,2'-MDI) and 4,4'-diphenylmethylene diisocyanate (4,4'-MDI); 4,4'-dibenzyl diisocyanate (4,4'-DBDI); toluene 2,6-diisocyanate (2,6-TDI); m-xylylene diisocyanate (m-XDI); ■ symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (H12MDI); ■ symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI); ■ unsymmetrical aromatic diisocyanate compounds, preferably: 2,4'-diphenylmethylene diisocyanate (2,4'-MDI); 2,4'-dibenzyl diisocyanate (2,4'-DBDI); toluene 2,4-diisocyanate (2,4-TDI); - a trimeric biurea compound, in particular a trimeric biurea compound of a compound chosen from: ■ symmetrical aromatic diisocyanate compounds, preferably: 2,2'-diphenylmethylene diisocyanate (2,2'-MDI) and 4,4'-diphenylmethylene diisocyanate (4,4'-MDI); 4,4'-dibenzyl diisocyanate (4,4'-DBDI); toluene 2,6-diisocyanate (2,6-TDI); m-xylylene diisocyanate (m-XDI); ■ symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (H12MDI); ■ symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI); ■ unsymmetrical aromatic diisocyanate compounds, preferably: 2,4'-diphenylmethylene diisocyanate (2,4'-MDI); 2,4'-dibenzyl diisocyanate (2,4'-DBDI); toluene 2,4-diisocyanate (2,4-TDI); ■ asymmetric alicyclic diisocyanate compounds, preferably isophorone diisocyanate (IPDI), preferably compound (a2) is selected from triphenylmethane-4,4',4”-triisocyanate, l,l',l”-methylidynetris (4-isocyanatobenzene), HDI isocyanurate, IPDI isocyanurate, PDI isocyanurate, HDI biurea trimer and IPDI biurea trimer, PDI biurea trimer.

3. Copolymer P according to one of claims 1 or 2 for which the polyhydroxylated compound (b) is chosen from: • a compound (b 1) of formula II: HO-Ln-OH (n) in which: - L independently represents an oxyalkylene residue; - n independently represents a number ranging from 30 to 1000; • a compound (bl) of formula II associated with a non-alkoxylated compound (b2) comprising at least three hydroxyl groups; a polyalkoxylated compound (b3) comprising at least three hydroxyl groups; combinations thereof.

4. Copolymer P according to one of claims 1 to 3 for which compound (b) is chosen from: • a compound (bl) of formula II in which: - L independently represents an oxyethylene residue; or - n independently represents a number ranging from 50 to 400, preferably from 100 to 300; or - L independently represents an oxyethylene residue and p independently represents a number ranging from 50 to 400, preferably from 100 to 300; • a compound (b2) comprising three hydroxyl groups, preferably chosen from glycerol, pentaerythritol and their combinations; • a compound (b3) different from compound (b2) and comprising three hydroxyl groups, preferably compound (b3) is polyethoxylated glycerol or polyethoxylated pentaerythritol.

5. Copolymer P according to one of claims 1 to 4 for which the compounds (b), (bl) or (b3) independently have a molar mass (Mw) measured by CES ranging from 1,500 to 40,000 g / mol, preferably from 2,000 to 20,000 g / mol, more preferably from 2,000 to 15,000 g / mol or from 2,000 to 12,000 g / mol.

6. Copolymer P according to one of claims 1 to 5 for which compound (c) is a compound of formula I in which: - R independently represents a group chosen from a linear C4-C24-alkyl group or a linear C4-C24-alkylene group, preferably a linear C6-C20-alkyl group or a linear C6-C20-alkylene group, more preferably a linear C12-C18-alkyl group or a linear C12-C18-alkylene group, much more preferably a linear C18-alkyl group; or - m independently represents 0 or a number from 2 to 50 or from 2 to 20 or from 2 to 10; or - Q represents an oxyethylene group or a combination of oxyethylene groups and oxypropylene groups, preferably in a molar proportion (oxyethylene groups / oxypropylene groups) ranging from 95 / 5 to 50 / 50, preferably ranging from 80 / 50 to 70 / 30 or from 65 / 35 to 55 / 45.

7. Copolymer P according to one of claims 1 to 6 for which the polymerization reaction involves: - from 10 to 79.9 mol% or from 10 to 74.5 mol%, preferably from 10 to 68 mol% or from 10 to 60 mol%, of monomer (a) or - from 20 to 89.9 mol% or from 25 to 89.5 mol%, preferably from 30 to 88 mol% or from 35 to 85 mol%, of monomer (b), or - from 0.1 to 70 mol% or from 0.5 to 65 mol%, preferably from 2 to 60 mol% or from 5 to 55 mol%, of monomer (c), relative to the total molar quantity of monomers (a), (b) and (c).

8. Copolymer P according to one of claims 1 to 7 for which the polymerization reaction also uses at least one hydrophobic compound (d) different from compound (c), preferably chosen from a compound of formula (III): R 5 -(OE)q-(OP)r-OH in which: - q and r, identical or different, independently represent 0 or an integer or decimal number less than 150, in particular q or r is different from 0, - OE independently represents a CH2CH2O group, - OP independently represents a group chosen from CH(CH3)CH2O and CH2CH(CH3)O, - R 1independently represents a linear or branched C4-C40-alkyl group, preferably a linear or branched C6-Cso-alkyl group, more preferably a linear or branched C6-C22-alkyl group, preferably less than 60 mol %, preferably from 0.05 to 60 mol %, in particular from 0.1 to 60 mol %, more preferably less than 50 mol %, preferably from 0.05 to 50 mol %, in particular from 0.1 to 50 mol %, of compound (d) relative to the total molar quantity of compounds involved.

9. Rheological control composition comprising at least one copolymer P according to one of claims 1 to 8, optionally treated in an acidic manner leading to a pH less than 8, preferably at a pH greater than 6, for example by means of an acid, in particular for example a carboxylic acid such as acetic acid or lactic acid. . Rheological control composition according to claim 9 also comprising at least one solvent, in particular water or a coalescence solvent, for example glycol, butyl glycol, butyl diglycol, monopropylene glycol, ethylene glycol, ethylene diglycol, “Dowanol” products whose CAS number is 34590-94-8, “Texanol” products whose CAS number is 25265-77-4; or combined with at least one additive chosen from an amphiphilic compound, in particular a surfactant compound, preferably a hydroxylated surfactant compound, for example alkyl-polyalkylene glycol, in particular alkyl-polyethylene glycol and alkyl-polypropylene glycol; a polysaccharide derivative, e.g., cyclodextrin, cyclodextrin derivative, polyethers, alkyl glucosides; a hydrotropic compound, an antifoaming agent, a biocidal agent and combinations thereof.

1. Aqueous formulation comprising:. - at least one composition according to one of claims 9 or 10; optionally - at least one organic or mineral pigment or organic, organo-metallic or mineral particles, for example calcium carbonate, talc, kaolin, mica, silicates, silica, metal oxides, in particular titanium dioxide, iron oxides; and optionally - at least one agent selected from a particle spacer agent, a dispersing agent, a steric stabilizing agent, an electrostatic stabilizing agent, an opacifying agent, a coloring agent, a solvent, a coalescing agent, an anti-foaming agent, a preservative, a biocidal agent, a spreading agent, a thickening agent, a film-forming copolymer and mixtures thereof. . Formulation according to claim 11 for coating, in particular an ink formulation, a varnish formulation, an adhesive formulation, a paint formulation, for example decorative paint or industrial paint. . Concentrated aqueous pigment paste comprising at least one copolymer P according to one of claims 1 to 8 and at least one organic or mineral colored pigment.

14. Method for controlling the viscosity of an aqueous composition comprising the addition of at least one copolymer P according to one of claims 1 to 8 in this composition.

15. Method according to claim 14 for which the aqueous composition is an aqueous formulation defined according to one of claims 11 or 12.

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