Dispersable Urethane Composite

Abstract

The invention relates to a composite in the form of a powder that is easily dispersible in an aqueous composition, particularly in a paint composition. The invention also provides a method for its preparation, which includes mixing the ingredients—a specific polymer with urethane functional groups and a specific surfactant compound—and then grinding this mixture.

Description

Title of the invention: DISPERSABLE URETHANUM COMPOSITE

[0001] The invention relates to a composite in the form of a powder that is easily dispersible in an aqueous composition, particularly in a paint composition. The invention also provides a method for its preparation, which includes mixing the ingredients, a particular polymer with methane functional groups and a specific surfactant compound, and then grinding this mixture.

[0002] Many technical fields require the use of aqueous compositions. In particular, aqueous ink compositions, aqueous coating compositions, including aqueous varnish compositions, and aqueous paint compositions, such as aqueous decorative paint compositions or aqueous industrial paint compositions, are known. Besides their functional properties, these aqueous compositions must have a texture suitable for their use or storage. In particular, they must have a suitable viscosity. Furthermore, these aqueous compositions must be usable under conditions that can vary widely. In particular, the viscosity of these aqueous compositions can vary or degrade.The functional properties of these aqueous compositions can therefore be altered if their rheological behavior is not suitable, for example to prevent sedimentation or phase separation phenomena during storage time, which can also manifest as viscosity variations. Such variations or degradations are particularly detrimental or damaging.

[0003] It is therefore particularly useful to have aqueous coating compositions, especially aqueous varnish or paint compositions, with a viscosity adapted to maintain their homogeneity and the integrity of their functional properties. Maintaining the viscosity and limiting the loss of viscosity of these aqueous compositions should be possible over a wide range of shear rates.

[0004] Consequently, many aqueous coating compositions utilize rheology-modifying agents. These agents should enable aqueous compositions to achieve the desired rheological properties over a wide range of shear rates. These agents should also improve the shear-thinning of these aqueous compositions by providing sufficient pseudo-plasticity, ensuring their stability and homogeneity during storage, facilitating their transfer onto application tools, and helping to limit the occurrence of runs after application. The compatibility of the various components of an aqueous coating composition must also be taken into account. In particular, It is important that the thickening agent and the pigments and binders used have good compatibility.

[0005] In addition to the functional properties they bring to aqueous compositions, these thickening agents must possess other properties useful during their preparation, packaging and transport as well as during their implementation.

[0006] Particularly for these reasons, liquid formulation of thickening agents for aqueous compositions is far from ideal. Indeed, the use of a liquid carrier, especially water, leads to drawbacks that must be effectively addressed. Besides complicating the preparation and transport of liquid thickening agents, such agents require special attention during their use in a paint composition.

[0007] Furthermore, since water provides a favorable environment for the growth of microorganisms, biocidal agents are essential in aqueous thickening agents. The quantities of biocidal agent used must therefore generally be deducted from the quantities of biocidal agent required for the aqueous paint composition. As a thickening agent in solid form requires very little or no biocidal agent, the quantities of biocidal agent available for the paint composition are even more flexible.

[0008] Furthermore, rheological control agents must be easy to handle and introduce into aqueous compositions, particularly coating compositions such as varnishes and paints. Specifically, it is important to be able to control the mixing, dispersion, and dissolution of solid rheological agents. In particular, efficient and sufficiently rapid dispersion of solid rheological agents in these aqueous compositions is desired.

[0009] It is also important to carefully control the particle size of solid rheological agents. Generally, excessively large particles can disrupt their dispersion in an aqueous medium, while insufficient particles can lead to the formation of agglomerates. Particles that are too small can also result in the presence of fine powders, which should be avoided, or even eliminated, in order to limit or prevent the problems they cause, both from a technical and industrial standpoint and for the safety of installations and personnel.

[0010] Known rheological control agents do not always provide a satisfactory solution to these various problems. Therefore, there is a need for an improved rheological control agent. Composite C according to the invention provides a solution to all or part of the problems of prior art agents.

[0011] The invention provides a prepared powder composite C: A- by mixing at least one non-ionic surfactant compound T and at least one water-soluble polymer P, obtained by a polymerization reaction: - of at least one compound chosen from a diisocyanate compound (a1), a polyisocyanate compound (a2) and their combinations, - of at least one polyhydroxylated compound (b), - of at least one compound (c) of formula I: [chem I] HO-R in which R independently represents a group selected from a linear Ci-C4o-alkyl group, a branched C3-C40-alkyl group, a C5-C40-cycloalkyl group, a linear C3-C40-alkylene group, a branched C3-C40-alkylene group, a C5-C40-aryl group and their combinations, B- by grinding the mixture of compound A and polymer P.

[0012] Preferably for the composite C according to the invention, the mixture A is made at a temperature above the melting point of the compound T. More preferably, the mixture A is made at a temperature above the melting point of the polymer P.

[0013] Preferably, mixture A is prepared at a temperature lower than the temperature of the polymerization reaction; more preferably, at a temperature ranging from 45°C to 85°C or from 50°C to 65°C.

[0014] Advantageously, the composite C according to the invention can be easily prepared. In particular, its preparation does not require a complex or sophisticated system or apparatus. Preferably, according to the invention, the mixture A is prepared using a stirrer. Also preferably, the resulting mixture is homogeneous. More preferably, this mixture is monophasic, preferably monophasic upon direct visual examination. Thus, upon visual examination performed more than 15 minutes after mixing A, no phase separation is visible.

[0015] During the preparation of the composite C according to the invention, the relative amounts of compound T and polymer P can vary quite widely. Preferably according to the invention, during mixing A, 1% to 40% by weight of compound T and 60% to 99% by weight of polymer P are mixed, relative to the total weight of compound T and polymer P. More preferably, 5% to 35% by weight of compound T and 65% to 95% by weight of polymer P are mixed, relative to the total weight of compound T and polymer P.

[0016] According to the invention, the composite C is in the form of solid particles. Advantageously, the composite C therefore comprises the compound T and the polymer P as its only ingredients. It may also comprise a very small amount of biocidal agent, in particular an isothiazolone derivative, especially 5-chloro-2-methyl-2H-isothiazol-3-one (CMIT), 2-methyl-2H-isothiazol-3-one (MIT), and combinations thereof. Preferably, the composite C according to the invention comprises an amount of biocidal agent less than 2% by weight, preferably less than 1.5% by weight or less than 1% by weight, more preferably less than 0.5% by weight, of the composite C, in particular CMIT or MIT or combinations thereof.

[0017] More preferably, the composite C according to the invention does not comprise any biocidal agent. In particular, it does not comprise any isothiazolone derivative, especially of CMIT or MIT or combinations thereof.

[0018] The ease of preparing composite C according to the invention also allows the use of conventional grinding equipment. Preferably, according to the invention, grinding is carried out using a grinder, preferably a knife mill, a disc mill, a vibrating mill, a ball mill, an impact mill, or an ultra-centrifugal mill. More preferably, grinding is carried out using a knife mill.

[0019] Essentially, according to the invention, the composite C according to the invention is in powder form. Preferably, the composite C according to the invention is in the form of particles whose median volume diameter, measured by sieving or by dry laser granulometry, ranges from 0.3 mm to 8 mm. More preferably, the median diameter of the particles ranges from 0.5 mm to 5 mm, preferably from 0.5 mm to 3 mm.

[0020] Advantageously, according to the invention, within the composite C according to the invention, the relative amounts of compound T and polymer P may vary. Preferably, the composite C comprises, relative to the total weight amount of compound T and polymer P, from 1% to 40% by weight of compound T and from 60% to 99% by weight of polymer P. More preferably, the composite C comprises from 5% to 35% by weight of compound T and from 65% to 95% by weight of polymer P relative to the total weight amount of compound T and polymer P.

[0021] Essentially, according to the invention, the composite C comprises at least one non-ionic surfactant compound T. Preferably, for the composite C according to the invention, compound T is a hydroxylated surfactant compound. More preferably, compound T is an alkyl-polyalkylene glycol, more preferably chosen from alkyl-polyethylene glycol and alkyl-polypropylene glycol, preferably alkyl- polyalkylene glycol. More preferably, it is chosen from C6-Ci6-alkyl-polyethylene glycol and C6-Ci6-alkyl-polypropylene glycol. Preferably, compound T is liquid at 30°C.

[0022] The methane-functionalized polymer P is another essential ingredient in obtaining the composite C according to the invention. The polymer P is prepared using compound (a1) or (a2) and compounds (b) and (c). Preferably for the composite C according to the invention, the diisocyanate compound (a1) is selected 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) (Hi2MDI); - symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI); - preferably dissymmetric aromatic diisocyanate compounds: . 2,4'-diphenylmethylene diisocyanate (2,4'-MDI); . 2,4'-dibenzyl diisocyanate (2,4'-DBDI); . toluene 2,4-diisocyanate (2,4-TDI); - dissymmetric alicyclic diisocyanate compounds, preferably isophorone diisocyanate (IPDI); - uretdiones, preferably uretdiones of symmetric aromatic diisocyanates, uretdiones of symmetric alicyclic diisocyanate compounds, uretdiones of symmetric aliphatic diisocyanate compounds, uretdiones of dissymmetric aromatic diisocyanate compounds, uretdiones of dissymmetric alicyclic diisocyanate compounds and their combinations; In a more preferred manner, compound (a) is chosen from IPDI, HDI, Hi2MDI and their combinations.

[0023] Preferably, for composite C according to the invention, the isocyanate compound (a2) is a polyisocyanate compound comprising strictly 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.

[0024] 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.

[0025] Also, and more preferably for composite C according to the invention, the polyisocyanate compound (a2) is selected from: - triphenylmethane-4,4',4”-triisocyanate or l,l',l”-methylidynetris (4-isocyanatobenzene); - an isocyanurate compound, in particular an isocyanurate compound of a compound selected 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) (Hi2MDI); * symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI); * dissymmetric 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 biurea trimer compound, in particular a biurea trimer compound of a compound selected 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) (Hi2MDI); * symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI); * dissymmetric aromatic diisocyanate compounds, preferably: . 2,4'-diphenylmethylene diisocyanate (2,4'-MDI); . 2,4'-dibenzyl düsocyanate (2,4'-DBDI); . toluene 2,4-düsocyanate (2,4-TDI); * dissymmetric alicyclic diisocyanate compounds, preferably isophorone diisocyanate (IPDI).

[0026] In a particularly preferred manner, the polyisocyanate compound (a2) is selected from triphenylmethane-4,4',4”-triisocyanate, l,l',l”-methylidynetris (4-isocyanatobenzene), an HDI isocyanurate, an IPDI isocyanurate, a PDI isocyanurate, an HDI biurea trimer and an IPDI biurea trimer, a PDI biurea trimer.

[0027] Preferably for composite C according to the invention, the polyhydroxylated compound (b) is a compound of formula II: [chem II] HO-U-OH in which L independently represents an oxyalkylene residue and n independently represents a number from 1 to 500.

[0028] Preferably according to the invention, L independently represents an oxyethylene residue or n independently represents a number from 10 to 400, preferably from 20 to 300. More preferably, L independently represents an oxyethylene residue and n independently represents a number from 20 to 400, preferably from 25 to 300.

[0029] Also preferably, compound (b) has an average molar mass (Mw), measured by CES, ranging from 500 g / mol to 20,000 g / mol, preferably from 800 g / mol to 15,000 g / mol or from 800 g / mol to 12,000 g / mol, more preferably from 1,500 g / mol to 15,000 g / mol or from 1,500 g / mol to 12,000 g / mol. Much more preferably, compound (b) has an average molar mass (Mw), measured by CES, ranging from 2,500 g / mol to 15,000 g / mol or from 2,500 g / mol to 10,000 g / mol.

[0030] Preferably for the composite C according to the invention, compound (c) is a compound of formula I in which R independently represents a group selected from a linear C32-alkyl Ci group, a branched C3-C32-alkyl group, a C5-C32-cycloalkyl group, a linear C3-C32-alkylene group, a branched C3-C32-alkylene group, a C5-C32-aryl group, and combinations thereof. More preferably, R independently represents a group selected from a linear C24-alkyl Ci group or a linear C3-C24-alkylene group, preferably a linear C4-C20-alkyl group or a linear C4-C20-alkylene group. Much more preferably, R represents a C6-C8-alkyl group linear or a linear C6-Ci8-alkylene group, even more preferably a linear C6-Ci6-alkyl group or a linear C6-Ci6-alkylene group.

[0031] Essentially, the composite C according to the invention is prepared using at least one water-soluble polymer P, obtained by a polymerization reaction of compound (a1) or (a2) and compounds (b) and (c). Preferably for the composite C according to the invention, the polymerization reaction is carried out in the polyhydroxylated compound (b), preferably in a molten medium of compound (b).

[0032] Also preferably according to the invention, the polymerization reaction uses 10 mol% to 79.9 mol% or 10 mol% to 74.5 mol%, preferably 10 mol% to 68 mol% or 10 mol% to 60 mol%, of monomer (a) relative to the total molar amount of monomers (a), (b) and (c).

[0033] According to the invention, the polymerization reaction can also implement from 20 mol% to 89.9 mol% or from 25 mol% to 89.5 mol%, preferably from 30 mol% to 88 mol% or from 35 mol% to 85 mol%, of monomer (b) or from 0.1 mol% to 70 mol% or from 0.5 mol% to 65 mol%, preferably from 2 mol% to 60 mol% or from 5 mol% to 55 mol%, of monomer (c), relative to the total molar amount of monomers (a), (b) and (c).

[0034] For the composite C according to the invention, the molar mass of the polymer P can vary. Preferably, for the composite C according to the invention, the polymer P has an average molar mass Mw, measured by CES, greater than 10,000 g / mol, preferably greater than 20,000 g / mol or 30,000 g / mol. Also preferably, the average molar mass Mw is less than 500,000 g / mol, preferably less than 300,000 g / mol or 200,000 g / mol. More preferably, polymer P has an average molar mass Mw, measured by CES, ranging from 10,000 g / mol to 500,000 g / mol, preferably from 20,000 g / mol to 300,000 g / mol or from 20,000 g / mol to 200,000 g / mol.

[0035] According to the invention, the polymer P generally has a polymolecularity index Ip, measured by CES, greater than 1.3 or greater than 1.5. Preferably, the polymolecularity index Ip is less than 5 or less than 4.

[0036] According to the invention, the molecular weight Mw and the polymolecularity index Ip are determined by Size Exclusion Chromatography (SEC). A test portion of the compound solution, corresponding to 90 mg of dry matter, is introduced into a 10 mL bottle. Mobile phase, supplemented with 0.04% dimethylformamide (DMF), is added up to a total mass of 10 g. The composition of this mobile phase is as follows: NaHCO3: 0.05 mol / L, NaNO3: 0.1 mol / L, triethanolamine: 0.02 mol / L, NaN3: 0.03 wt%. The SEC system consists of a Waters 510 isocratic pump, the flow rate of which is set at 0.8 mL / min, and a sampler. The CES setup consists of Waters 717+ samples, a furnace containing a 6 cm long, 40 mm internal diameter Waters Guard Column Ultrahydrogel pre-column, followed by a 30 cm long, 7.8 mm internal diameter Waters Ultrahydrogel linear column. Detection is performed using a Waters RI 410 differential refractometer. The furnace is heated to 60°C and the refractometer to 45°C. The CES setup is calibrated with a series of sodium polyacrylate standards supplied by Polymer Standards Service with peak molecular weights ranging from 900 g / mol to 2,250,000 g / mol and polymolecularity indices ranging from 1.4 to 1.7. The calibration curve is linear and takes into account the correction obtained using the flow marker: dimethylformamide (DMF).The acquisition and processing of the chromatogram are carried out using the software "PSS WinGPC Scientific" v 4.02. The resulting chromatogram is integrated into the area corresponding to molecular weights greater than 250 g / mol.

[0037] Advantageously, the composite C according to the invention can be prepared in a simple manner. Thus, the invention also provides a method for preparing a composite C according to the invention comprising: A- the mixture of at least one non-ionic surfactant compound T and at least one water-soluble polymer P, obtained by a polymerization reaction of: - at least one diisocyanate compound (a), - at least one polyhydroxylated compound (b), - at least one compound (c) of formula I: [chem I] HO-R in which R independently represents a group chosen from a linear Ci-C40-alkyl group, a branched C3-C4o-alkyl group, a C5-C40-cycloalkyl group, a linear C3-C40-alkylene group, a branched C3-C40-alkylene group, a C5-C4o-aryl group and their combinations, B- the grinding of the mixture of compound A and polymer P.

[0038] According to the invention, the particular, advantageous or preferred characteristics of composite C define methods for its preparation which are also particular, advantageous or preferred.

[0039] The composite C according to the invention possesses properties useful in a number of technical fields that require the use of an aqueous composition. In particular, the composite C according to the invention makes it possible to act effectively on the rheology of an aqueous composition, and especially of an aqueous paint composition. The invention therefore provides a method for controlling the rheology of a An aqueous paint composition comprising the addition, preferably under stirring, of at least one composite C according to the invention to an aqueous paint composition. The resulting composition is also part of the invention. Thus, the invention also provides an aqueous composition, preferably an ink composition, varnish composition, adhesive composition, or paint composition, for example, decorative or industrial paint, comprising: * at least one composite C according to the invention, * at least one binding agent B, and optionally * at least one organic, organometallic or mineral pigment Q, preferably a pigment chosen from calcium carbonate, talc, kaolin, mica, silicates, silica, metallic oxides, in particular titanium dioxide, iron oxides.

[0040] Preferably for this composition according to the invention, the binding agent B is a sterically modified binding compound. Preferably, the binding agent B is selected from a vinyl acetate homopolymer; a vinyl acetate copolymer; a vinyl versatate homopolymer; a vinyl versatate copolymer; and combinations thereof. More preferably, the binding agent B is selected from: - a vinyl acetate homopolymer; - a copolymer comprising at least vinyl acetate and ethylene, a vinyl acetate and acrylate copolymer, a vinyl acetate and methacrylate copolymer, a vinyl acetate, ethylene and acrylate copolymer, a vinyl acetate, ethylene and methacrylate copolymer, a vinyl acetate, acrylate and methacrylate copolymer; - a vinyl versatate homopolymer; - a copolymer of vinyl versatate and ethylene, a copolymer of vinyl versatate and acrylate, a copolymer of vinyl versatate and methacrylate, a copolymer of vinyl versatate, ethylene and acrylate, a copolymer of vinyl versatate, ethylene and methacrylate, a copolymer of vinyl versatate, acrylate and methacrylate; - a copolymer of vinyl acetate and vinyl versatate, a copolymer of vinyl acetate, vinyl versatate and ethylene, a copolymer of vinyl acetate, vinyl versatate and acrylate, a copolymer of vinyl acetate, vinyl versatate and methacrylate, a copolymer of vinyl acetate, vinyl versatate, ethylene and acrylate, a copolymer of vinyl acetate, vinyl versatate, ethylene and methacrylate, a copolymer of vinyl acetate, vinyl versatate, ethylene, acrylate and methacrylate and - their combinations.

[0041] Preferably according to the invention, this composition comprises from 0.1% by dry weight to 4% by dry weight of composite C, from 5% by dry weight to 20% by weight dry binder B, 3% to 15% to 64.9% to 71.9% water by dry weight. It may also optionally include at least one agent selected from a particle spacer, dispersing agent, steric stabilizer, electrostatic stabilizer, opacifier, colorant, solvent, coalescing agent, antifoaming agent, preservative, biocide, spreading agent, thickener, film-forming copolymer, and mixtures thereof.

[0042] The invention also provides a concentrated aqueous pigment paste comprising at least one composite C according to the invention and at least one colored organic or mineral pigment.

[0043] The invention also relates to a method for controlling the viscosity of an aqueous composition comprising adding to this composition at least one composite according to the invention.

[0044] The invention very effectively allows for the simultaneous and controlled introduction of compound T and polymer P into an aqueous composition, particularly to improve viscosity control of that composition. Thus, the invention provides a method for controlling the viscosity of an aqueous composition comprising the simultaneous addition to that composition of compound T and polymer P in the form of a composite according to the invention.

[0045] Preferably according to the invention, the method for controlling the viscosity of an aqueous composition comprises the direct introduction of the powdered composite C. This method may also comprise the indirect introduction of the composite, which is then first combined with a liquid support, preferably water, alone or combined with at least one organic solvent.

[0046] The particular, advantageous or preferred characteristics of the composite C according to the invention define methods for its use as well as paint compositions or pigment pastes which are also particular, advantageous or preferred.

[0047] The various aspects of the invention can be illustrated by examples.

[0048] EXAMPLES

[0049] Preparation and characterization of Cl to C3 compounds according to the invention

[0050] For the preparation of the PI to P3 polymers according to the invention, the following compounds are used: - compound al-1: isophorone diisocyanate (IPDI), - compound bl: polyethylene glycol with a molecular mass of 10,000 g / mol, - compound cl: monoalcohol of formula I in which R represents a linear Ci2-alkyl group, - compound c2: monoalcohol of formula I in which R represents a tristyrylphenyl group ethoxylated 2.6 times on average, - compound c3: monoalcohol of formula I in which R represents a cardanyl group ethoxylated 4 times.

[0051] Preparation and characterization of the Cl compound according to the invention

[0052] In a beaker equipped with a hot plate and magnetic stirrer, a mixture of compound (cl) (16.00 g) and an 1,8-diazabicyclo[5.4.0]undec-7-ene catalyst (“Polycat DBU” - 0.18 g) is added to compound (al-1) (19.10 g) preheated to 25°C. The addition is carried out under stirring at 90°C for 15 minutes to obtain a first mixture.

[0053] In a 2 L reactor equipped with an oil bath and mechanical stirring, the compound (bl) (272.52 g) is introduced and heated to 90°C. A catalyst (“Polycat DBU” - 0.32 g) is added, as well as the first mixture (31.22 g). The reaction is carried out at 105°C for one hour with stirring to obtain the PI polymer according to the invention.

[0054] The PI polymer is cooled to 60°C and a surfactant compound Tl (10-fold ethoxylated C8 fatty alcohol – “Surfaline Ox 1008” – 76.02 g) is introduced while stirring. This mixture is solidified by cooling to room temperature on an aluminum plate. It is then ground using a knife mill (“Vorwerk Thermomix”) for 30 seconds, gradually increasing the power up to the maximum power to obtain the Cl composite according to the invention, the median volume diameter of particles of which, measured by dry laser granulometry, is 1.2 mm.

[0055] Preparation and characterization of the C2 composite according to the invention

[0056] In a 2 L reactor equipped with a hot plate and mechanical stirring, compound (bl) (263.69 g) is introduced and heated to 90°C. Compound (c2) (27.46 g) is then introduced, and the mixture is dried before the introduction of a catalyst (“Polycat DBU” - 0.17 g), followed by compound (al-1) (16.86 g). The reaction is carried out at 105°C for one hour with stirring to obtain polymer P2 according to the invention.

[0057] The P2 polymer is cooled to 60°C and a surfactant compound Tl (10-fold ethoxylated C8 fatty alcohol – “Surfaline Ox 1008” – 77.05 g) is introduced while stirring. This mixture is solidified by cooling to room temperature on an aluminum plate. It is then ground using a knife mill (“Vorwerk Thermomix”) for 30 seconds, gradually increasing the power up to the maximum power to obtain the C2 composite according to the invention, the median volume diameter of particles of which, measured by dry laser granulometry, is 1.5 mm.

[0058] Preparation and characterization of the C3 composite according to the invention

[0059] In a 2 L reactor equipped with a hot plate and mechanical stirring, compound (bl) (262.27 g) is introduced and heated to 90°C. The compound (c3) (27.73 g) is introduced and the mixture is dried before the introduction of a catalyst (“Polycat DBU” - 0.17 g), followed by compound (al-1) (17.03 g). The reaction is carried out at 105°C for 30 minutes with stirring to obtain the P3 polymer according to the invention.

[0060] The P3 polymer is cooled to 60°C and a surfactant compound T2 (5-fold ethoxylated C6 fatty alcohol “Emulan HE 51” - 102.40 g) is introduced while stirring. This mixture is solidified by cooling to room temperature on an aluminum plate. It is then ground at a rotational speed of 3,000 rpm using a knife mill (“Retsch SM 300”) equipped with a V-rotor, a bottom sieve (4 mm mesh), and a cyclone system under vacuum to obtain the C3 composite according to the invention, the median volume diameter of particles of which, measured by dry laser granulometry, is 1.2 mm.

[0061] Preparation and characterization of aqueous compositions according to the invention

[0062] In a beaker equipped with a magnetic stirrer, the Cl composite (3.0 g) is mixed with 197.0 g of water under stirring at 700 rpm and 25°C. After 15 minutes, the resulting aqueous composition is visually homogeneous.

[0063] Similarly, aqueous compositions are prepared by replacing the Cl composite with the C2 (2.0 g) and C3 (2.0 g) composites respectively in 198.0 g of water. The compositions comprising the C2 and C3 composites are visually homogeneous after less than 30 minutes.

Claims

Demands

1. Powdered composite C prepared: A- by mixing at least one non-ionic surfactant compound T and at least one water-soluble polymer P, obtained by a polymerization reaction of: - at least one compound selected from a diisocyanate compound (a1), a polyisocyanate compound (a2) and their combinations, - at least one polyhydroxylated compound (b), - at least one compound (c) of formula I: [chem I] HO-R in which R independently represents a group selected from a linear Ci-C4o-alkyl group, a branched C3-C40-alkyl group, a C5-C4o-cycloalkyl group, a linear C3-C40-alkylene group, a branched C3-C40-alkylene group, a C5-C40-aryl group and their combinations, B- by grinding the mixture of compound T and polymer P.

2. Composite C according to claim 1, wherein: * the mixture A is prepared at: - a temperature above the melting point of compound T, or - a temperature above the melting point of polymer P, preferably - a temperature below the polymerization reaction temperature; more preferably at: - a temperature ranging from 45°C to 85°C or from 50°C to 65°C; or wherein: * the mixture A is prepared using a stirrer, or * the mixture is homogeneous, preferably the mixture is monophasic, preferably monophasic upon direct visual examination; or wherein: * are mixed: - from 1% by weight to 40% by weight of compound T and from 60% by weight to 99% by weight of polymer P, relative to the total amount by weight of compound T and polymer P; preferably: - from 5% by weight to 35% by weight of compound T and from 65% by weight to 95% by weight of polymer P, relative to the total quantity by weight of compound T and polymer P;or for which:; * the grinding is carried out using a grinder, preferably a knife grinder, a disc grinder, a vibrating grinder, a ball mill, an impact grinder, an ultra-centrifugal grinder, more preferably a knife grinder.

3. Composite C according to claim 1 or 2: * which is in the form of particles having a median volume diameter, measured by sieving or dry laser granulometry, of 0.3 mm to 8 mm or 0.5 mm to 5 mm, preferably 0.5 mm to 3 mm; or * comprising, relative to the total weight of compound T and polymer P, 1% to 40% by weight of compound T and 60% to 99% by weight of polymer P; preferably 5% to 35% by weight of compound T and 65% to 95% by weight of polymer P; or * comprising a quantity of biocidal agent less than 2% by weight, preferably less than 1.5% by weight or less than 1% by weight, more preferably less than 0.5% by weight of composite C, in particular of derivative with isothiazolone group, particularly of 5-chloro-2-methyl-2H-isothiazol-3-one (CMIT), of 2-methyl-2H-isothiazol-3-one (MIT) and their combinations;or * not containing any biocidal agent, preferably no derivative with an isothiazolone group, in particular of CMIT or MIT or their combinations.;

4. Composite C according to any one of claims 1 to 3 wherein compound T is a hydroxylated surfactant compound, preferably alkyl-polyalkylene glycol, more preferably alkyl-polyethylene glycol and alkyl-polypropylene glycol, preferably alkyl-polyalkylene glycol, much more preferably C6-Ci6-alkyl-polyethylene glycol and C6-Ci6-alkyl-polypropylene glycol; or wherein compound T is liquid at 30°C.

5. Composite C according to any one of claims 1 to 4, wherein: * the diisocyanate compound (al) is selected 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) (Hi2MDI); - symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI); - preferably dissymmetric aromatic diisocyanate compounds: . 2,4'-diphenylmethylene diisocyanate (2,4'-MDI); . 2,4'-dibenzyl diisocyanate (2,4'-DBDI); . toluene 2,4-diisocyanate (2,4-TDI); - dissymmetric alicyclic diisocyanate compounds, preferably isophorone diisocyanate (IPDI), - uretdiones, preferably uretdiones of symmetrical aromatic diisocyanates, uretdiones of symmetrical alicyclic diisocyanate compounds, uretdiones of symmetrical aliphatic diisocyanate compounds, uretdiones of unsymmetrical aromatic diisocyanate compounds, uretdiones of unsymmetrical alicyclic diisocyanate compounds and combinations thereof; more preferably, compound (a) is selected from IPDI, HDI, Hi2MDI and combinations thereof; or * the isocyanate compound (a2) is a polyisocyanate compound 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 The polyisocyanate compound (a2) is 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 selected 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) (Hi2MDI); * symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI); * dissymmetric 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 biurea trimer compound, in particular a biurea trimer compound of a compound selected 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) (Hi2MDI); * symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI); * dissymmetric 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); * dissymmetric alicyclic diisocyanate compounds, preferably isophorone diisocyanate (IPDI), preferably, the polyisocyanate compound (a2) is selected from triphenylmethane-4,4',4"-triisocyanate, 1,1',1"-methylidynetris (4-isocyanatobenzene), an HDI isocyanurate, an IPDI isocyanurate, a PDI isocyanurate, an HDI biurea trimer and an IPDI biurea trimer, a PDI biurea trimer; or * The polyhydroxylated compound (b) is a compound of formula II: [chem II] HO-U-QH in which: - L independently represents an oxyalkylene residue and n independently represents a number from 1 to 500; preferably where: - L independently represents an oxyethylene residue, or n independently represents a number from 10 to 400, preferably from 20 to 300; or - L independently represents an oxyethylene residue and n independently represents a number from 20 to 400, preferably from 25 to 300; or * Compound (b) has an average molar mass (Mw), measured by CES, ranging from 500 g / mol to 20,000 g / mol, preferably from 800 g / mol to 15,000 g / mol or from 800 g / mol to 12,000 g / mol, more preferably from 1,500 g / mol to 15,000 g / mol or from 1,500 g / mol to 12,000 g / mol, much more preferably from 2,500 g / mol to 15,000 g / mol or from 2,500 g / mol to 10,000 g / mol; or * Compound (c) is a compound of formula I in which: - R independently represents a group selected from a linear C1-C32-alkyl group, a branched C3-C32-alkyl group, a C5-C32-cycloalkyl group, a linear C3-C32-alkylene group, a branched C3-C32-alkylene group, a C5-C32-aryl group and combinations thereof; or - R independently represents a group chosen from a linear C1-C24-alkyl group or a linear C3-C24-alkylene group, preferably a linear C4-C20-alkyl group or a linear C4-C20-alkylene group, more preferably a linear C6-C18-alkyl group or a C6-C18-alkylene group linear, much more preferably a linear C6-Ci6-alkyl group or a linear C6-Ci6-alkylene group.

6. Composite C according to any one of claims 1 to 5 wherein: * the polymerization reaction is carried out in the polyhydroxylated compound (b), preferably in a molten medium of the compound (b); or * the polymerization reaction involves: - 10 mol% to 79.9 mol% or 10 mol% to 74.5 mol%, preferably 10 mol% to 68 mol% or 10 mol% to 60 mol%, of monomer (a) or - 20 mol% to 89.9 mol% or 25 mol% to 89.5 mol%, preferably 30 mol% to 88 mol% or 35 mol% to 85 mol%, of monomer (b), or - 0.1 mol% to 70 mol% or 0.5 mol% to 65 mol%, preferably 2 mol% to 60 mol% or 5 mol% to 55 mol%, of monomer (c), relative to the total mol% of monomers (a), (b) etc).

7. Composite C according to any one of claims 1 to 6 wherein: * the polymer P has an average molar mass Mw, measured by CES, greater than 10,000 g / mol, preferably greater than 20,000 g / mol or 30,000 g / mol, or an average molar mass Mw less than 500,000 g / mol, preferably less than 300,000 g / mol or 200,000 g / mol; or wherein: * the polymer P has an average molar mass Mw, measured by CES, ranging from 10,000 g / mol to 500,000 g / mol, preferably from 20,000 g / mol to 300,000 g / mol or from 20,000 g / mol to 200,000 g / mol; or for which: * polymer P has a polymolecularity index Ip, measured by CES, of less than 5 or less than 4, ; or has a polymolecularity index Ip greater than 1.3 or greater than 1.

5.

8. Method of preparing a composite C according to any one of claims 1 to 7 comprising: A- the mixture of at least one non-ionic surfactant compound T and at least one water-soluble polymer P, obtained by a polymerization reaction of: - at least one diisocyanate compound (a), - at least one polyhydroxylated compound (b), - at least one compound (c) of formula I: [chem I] HO-R in which R independently represents a group chosen from a linear Ci-C40-alkyl group, a branched C3-C40-alkyl group, a C5-C4o-cycloalkyl group, a linear C3-C4o-alkylene group, a branched C3-C40-alkylene group, a C5-C40-aryl group and their combinations, B- the grinding of the mixture of compound T and polymer P.

9. Method for controlling the rheology of an aqueous paint composition comprising the addition, preferably the addition under stirring, of at least one composite C according to any one of claims 1 to 7 in an aqueous paint composition.

10. Aqueous composition, preferably an ink composition, varnish composition, adhesive composition, paint composition, for example decorative paint or industrial paint, comprising: * at least one composite C according to any one of claims 1 to 7, * at least one binding agent B, and optionally * at least one organic, organometallic or mineral pigment Q, preferably a pigment selected from calcium carbonate, talc, kaolin, mica, silicates, silica, metal oxides, in particular titanium dioxide, iron oxides.

11. Composition according to claim 10 wherein the binding agent B is a sterically modified binding compound, preferably a binding agent B selected from a vinyl acetate homopolymer; a vinyl acetate copolymer; a vinyl versatate homopolymer; a vinyl versatate copolymer and combinations thereof; more preferably a binding agent B selected from: - a vinyl acetate homopolymer; - a copolymer comprising at least vinyl acetate and ethylene, a vinyl acetate and acrylate copolymer, a vinyl acetate and methacrylate copolymer, a vinyl acetate, ethylene and acrylate copolymer, a vinyl acetate, ethylene and methacrylate copolymer, a vinyl acetate, acrylate and methacrylate copolymer; - a vinyl versatate homopolymer; - a copolymer of vinyl versatate and ethylene, a copolymer of vinyl versatate and acrylate, a copolymer of vinyl versatate and methacrylate, a copolymer of vinyl versatate, ethylene and acrylate, a copolymer of vinyl versatate, ethylene and methacrylate, a copolymer of vinyl versatate, acrylate and methacrylate; - a copolymer of vinyl acetate and vinyl versatate, a copolymer of vinyl acetate, vinyl versatate and ethylene, a copolymer of vinyl acetate, vinyl versatate and acrylate, a copolymer of vinyl acetate, vinyl versatate and methacrylate, a copolymer of vinyl acetate, vinyl versatate, ethylene and acrylate, a copolymer of vinyl acetate, vinyl versatate, ethylene and methacrylate, a copolymer of vinyl acetate, vinyl versatate, ethylene, acrylate and methacrylate and - their combinations.

12. Composition according to any one of claims 10 or 11 comprising: - from 0.1% by dry weight to 4% by dry weight of composite C, - from 5% by dry weight to 20% by dry weight of binder B, - from 3% by dry weight to 15% by dry weight of pigment Q, - from 64.9% by dry weight to 71.9% by dry weight of water; and optionally comprising at least one agent selected from a particle spacer, a dispersing agent, a steric stabilizer, an electrostatic stabilizer, an opacifying agent, a coloring agent, a solvent, a coalescing agent, an antifoaming agent, a preservative, a biocidal agent, a spreading agent, a thickening agent, a film-forming copolymer and mixtures thereof.

13. Concentrated aqueous pigment paste comprising at least one composite C according to any one of claims 1 to 7 and at least one colored organic or mineral pigment.

14. Method for controlling the viscosity of an aqueous composition comprising the simultaneous addition to this composition of a compound T and a polymer P in the form of a composite according to any one of claims 1 to 7, preferably by direct introduction of the powdered composite C or by indirect introduction of the composite previously combined with a liquid support, preferably water, alone or combined with at least one organic solvent.