Dispersible urethane composite

Abstract

The invention relates to a composite in the form of a powder that is readily dispersible in an aqueous composition, in particular in a paint composition. The invention also relates to a method for producing said composite, which comprises mixing ingredients, namely a particular polymer having urethane functions and a specific surfactant compound, and then grinding said mixture.

Description

[0001] DISPERSABLE URETHANE COMPOSITE

[0002] 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 methane functional groups and a specific surfactant compound—and then grinding this mixture.

[0003] 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 (for example, aqueous decorative paint compositions or aqueous industrial paint compositions) are well-known. Beyond their functional properties, these aqueous compositions must have a texture suitable for their intended use or storage. Specifically, they must have an appropriate viscosity. Furthermore, these aqueous compositions must be usable under conditions that can vary widely. In particular, the viscosity of these aqueous compositions can fluctuate 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 during storage, which can also manifest as viscosity variations. Such variations or degradations are particularly detrimental or damaging.

[0004] It is therefore particularly useful to have access to aqueous coating compositions, especially aqueous varnishes or paints, with a viscosity adapted to maintain their homogeneity and the integrity of their functional properties. Maintaining viscosity and limiting viscosity loss in these aqueous compositions should be possible over a wide range of shear rates.

[0005] Consequently, many aqueous coating compositions utilize rheology-modifying agents. These agents are designed to impart the desired rheological properties to the aqueous compositions across a wide range of shear rates. They should also enhance the shear-thinning properties of these compositions by providing sufficient pseudo-plasticity, ensuring their stability and homogeneity during storage, facilitating their transfer onto application tools, and helping to minimize drips after application. The compatibility of the various components within an aqueous coating composition must also be considered. In particular, it is crucial that the thickening agent, pigments, and binders used are compatible.

[0006] 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.

[0007] For these reasons, among others, liquid formulation of thickening agents for aqueous compositions is far from ideal. Indeed, the use of a liquid carrier, particularly 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 paint formulations.

[0008] 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 solid thickening agent requires very little or no biocidal agent, the quantities of biocidal agent available for the paint composition are even more flexible. Moreover, rheological control agents must be easy to handle and incorporate into aqueous compositions, particularly in 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, we are looking for an efficient and sufficiently rapid dispersion of solid rheological agents in these aqueous compositions.

[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, to limit or prevent the problems they cause, both from a technical and industrial standpoint, as well as for the safety of installations and personnel.

[0010] Document WO 2023187265 concerns the use of naturally derived polyalkoxylated compounds to prepare polyurethanes that can be applied in liquid or solid form. Document WO 2011030197 describes water-soluble thickening polyurethanes for water-based paints.

[0011] 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 some of the problems of prior art agents. The invention provides a prepared powdered composite C:

[0012] A- by mixing at least one non-ionic surfactant compound T and at least one water-soluble polymer P, obtained by a polymerization reaction:

[0013] - of at least one compound chosen from a diisocyanate compound (a1), a polyisocyanate compound (a2) and their combinations,

[0014] - of at least one polyhydroxylated compound (b),

[0015] - of at least one compound (c) of formula I:

[0016] HO-R

[0017]

[0018] in which R independently represents a group chosen from a linear C1-C4o-alkyl group, a branched C3-C4o-alkyl group, a C5-C4o-cycloalkyl group, a linear C3-C4o-alkylene group, a branched C3-C4o-alkylene group, a C5-C4o-aryl group and their combinations,

[0019] B- by grinding the mixture of compound T and polymer P.

[0020] 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. Preferably, the mixture A is made at a temperature below 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.

[0021] 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, 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. 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, from 1% by weight to 40% by weight of compound T and from 60% by weight to 99% by weight of polymer P are mixed, relative to the total weight of compound T and polymer P.Preferably, 5% by weight to 35% by weight of compound T and 65% by weight to 95% by weight of polymer P are mixed, relative to the total amount by weight of compound T and polymer P.

[0022] According to the invention, the composite C is in the form of solid particles. Advantageously, the composite C comprises the compound T and the polymer P as its only ingredients. It may also include 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.

[0023] Preferably, the composite C according to the invention does not comprise any biocidal agent. In particular, it does not comprise any derivative with an isothiazolone group, especially of CMIT or MIT or combinations thereof.

[0024] 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.

[0025] Essentially, according to the invention, composite C is in powder form. Preferably, composite C is in the form of particles whose median volume diameter, measured by sieving or dry laser granulometry, ranges from 0.3 mm to 8 mm. More preferably, the median particle diameter ranges from 0.5 mm to 5 mm, and more preferably from 0.5 mm to 3 mm.

[0026] Advantageously, according to the invention, within the composite C according to the invention, the relative amounts of compound T and polymer P can vary. Preferably, the composite C comprises, relative to the total weight 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 of compound T and polymer P.

[0027] Essentially, according to the invention, the composite C comprises at least one nonionic 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, and even more preferably from alkyl-polyalkylene glycol. Most preferably, it is chosen from C0-C10-alkyl-polyethylene glycol and C0-C10-alkyl-polypropylene glycol. Preferably, compound T is liquid at 30°C.

[0028] The methane-functionalized polymer P is another essential ingredient in obtaining the composite C according to the invention. 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:

[0029] - symmetrical aromatic diisocyanate compounds, preferably:

[0030] . 2,2'-diphenylmethylene diisocyanate (2,2'-MDI) and 4,4'-diphenylmethylene diisocyanate (4,4'-MDI);

[0031] . 4,4'-dibenzyl diisocyanate (4,4'-DBDI);

[0032] toluene 2,6-diisocyanate (2,6-TDI);

[0033] . m-xylylene diisocyanate (m-XDI);

[0034] - symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (H12MDI);

[0035] - symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI);

[0036] - preferably dissymmetric aromatic diisocyanate compounds:

[0037] . 2,4'-diphenylmethylene diisocyanate (2,4'-MDI);

[0038] . 2,4'-dibenzyl diisocyanate (2,4'-DBDI);

[0039] . toluene 2,4-diisocyanate (2,4-TDI);

[0040] - dissymmetric alicyclic diisocyanate compounds, preferably isophorone diisocyanate (IPDI);

[0041] - uretdiones, preferably uretdiones of symmetric aromatic diisocyanates, uretdiones of symmetric alicyclic diisocyanate compounds, uretdiones of symmetric aliphatic diisocyanate compounds, uretdiones of unsymmetric aromatic diisocyanate compounds, uretdiones of unsymmetric alicyclic diisocyanate compounds and their combinations; more preferably, the compound (al) is chosen from IPDI, HDI, H12MDI and their combinations.

[0042] 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 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.

[0043] In a much more preferred manner, 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.

[0044] Also, and more preferably for composite C according to the invention, the polyisocyanate compound (a2) is selected from:

[0045] - triphenylmethane-4,4',4”-triisocyanate or l,l',l”-methylidynetris (4-isocyanatobenzene);

[0046] - an isocyanurate compound, in particular an isocyanurate compound of a compound selected from:

[0047] * Symmetrical aromatic diisocyanate compounds, preferably:

[0048] 2,2'-diphenylmethylene diisocyanate (2,2'-MDI) and 4,4'-diphenylmethylene diisocyanate (4,4'-MDI);

[0049] . 4,4'-dibenzyl diisocyanate (4,4'-DBDI);

[0050] . toluene 2,6-diisocyanate (2,6-TDI);

[0051] . m-xylylene diisocyanate (m-XDI);

[0052] * symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (H12MDI);

[0053] * symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI);

[0054] * asymmetrical aromatic diisocyanate compounds, preferably:

[0055] . 2,4'-diphenylmethylene diisocyanate (2,4'-MDI); . 2,4'-dibenzyl diisocyanate (2,4'-DBDI);

[0056] . toluene 2,4-diisocyanate (2,4-TDI);

[0057] - a biurea trimer compound, in particular a biurea trimer compound of a compound selected from:

[0058] * Symmetrical aromatic diisocyanate compounds, preferably:

[0059] 2,2'-diphenylmethylene diisocyanate (2,2'-MDI) and 4,4'-diphenylmethylene diisocyanate (4,4'-MDI);

[0060] . 4,4'-dibenzyl diisocyanate (4,4'-DBDI);

[0061] . toluene 2,6-diisocyanate (2,6-TDI);

[0062] . m-xylylene diisocyanate (m-XDI);

[0063] * symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (H12MDI);

[0064] * symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI);

[0065] * asymmetrical aromatic diisocyanate compounds, preferably:

[0066] . 2,4'-diphenylmethylene diisocyanate (2,4'-MDI);

[0067] . 2,4'-dibenzyl diisocyanate (2,4'-DBDI);

[0068] . toluene 2,4-diisocyanate (2,4-TDI);

[0069] * dissymmetric alicyclic diisocyanate compounds, preferably isophorone diisocyanate (IPDI).

[0070] Particularly preferred, 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.

[0071] Preferably for composite C according to the invention, the polyhydroxylated compound (b) is a compound of formula II:

[0072] HO- -OH (j

[0073] in which L independently represents an oxyalkylene residue and n independently represents a number from 1 to 500.

[0074] 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. Also preferably, the compound (b) has an average molar mass (Mw), measured by CES, from 500 g / mol to 20000 g / mol, preferably from 800 g / mol to 15000 g / mol or from 800 g / mol to 12000 g / mol, more preferably from 1500 g / mol to 15000 g / mol or from 1500 g / mol to 12000 g / mol. Much more preferentially, compound (b) has an average molar mass (Mw), measured by CES, ranging from 2500 g / mol to 15,000 g / mol or from 2,500 g / mol to 10,000 g / mol.

[0075] Preferably, for 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-C2o-alkyl group or a linear C4-C2o-alkylene group. Much more preferably, R represents a linear Cô-Cis-alkyl group or a linear Cô-Cis-alkylene group, even more preferably a linear Cô-Ci6-alkyl group or a linear Cô-Ciô-alkylene group.

[0076] 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).

[0077] Also preferably according to the invention, the polymerization reaction employs 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).

[0078] According to the invention, the polymerization reaction can also utilize 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 molar amount of monomers (a), (b), and (c). For the composite C according to the invention, the molar mass of polymer P can vary. Preferably, for composite C according to the invention, 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 10000 g / mol to 500000 g / mol, preferably from 20000 g / mol to 300000 g / mol or from 20000 g / mol to 200000 g / mol.

[0079] 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.

[0080] 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 CES system consists of a Waters 510 isocratic pump with a flow rate set at 0.8 mL / min, a Waters 717+ autosampler, and 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 410 RI differential refractometer. The furnace is heated to 60°C and the refractometer to 45°C. The CES device is calibrated with a series of sodium polyacrylate standards supplied by Polymer Standards Service with peak molecular weights between 900 g / mol and 2250000 g / mol and polymolecularity indices between 1.4 and 1.7.The calibration curve is linear and takes into account the correction obtained using the flow marker: dimethylformamide (DMF). Acquisition and processing of the chromatogram are performed using the software "PSS WinGPC Scientific" v 4.02. The resulting chromatogram is integrated into the region corresponding to molecular weights greater than 250 g / mol. Advantageously, the composite C according to the invention can be prepared simply. Thus, the invention also provides a method for preparing a composite C according to the invention comprising:

[0081] A- a mixture of at least one non-ionic surfactant compound T and at least one water-soluble polymer P, obtained by a polymerization reaction:

[0082] - of at least one diisocyanate compound (a),

[0083] - of at least one polyhydroxylated compound (b),

[0084] - of at least one compound (c) of formula I:

[0085] HO-R (j)

[0086] in which R independently represents a group chosen from a linear C1-C4o-alkyl group, a branched C3-C4o-alkyl group, a C5-C4o-cycloalkyl group, a linear C3-C4o-alkylene group, a branched C3-C4o-alkylene group, a C5-C4o-aryl group and their combinations,

[0087] B- the grinding of the mixture of compound T and polymer P.

[0088] 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.

[0089] Composite C according to the invention possesses properties useful in many technical fields that require the use of an aqueous composition. In particular, Composite C according to the invention makes it possible to effectively control the rheology of an aqueous composition, and especially of an aqueous paint composition. The invention therefore provides a method for controlling the rheology of 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:

[0090] * at least one composite C according to the invention,

[0091] * 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.

[0092] 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:

[0093] - a vinyl acetate homopolymer;

[0094] - 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;

[0095] - a vinyl versatate homopolymer;

[0096] - 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;

[0097] - 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.

[0098] 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 dry weight of binding agent B, from 3% by dry weight to 15% by dry weight of pigment Q, and from 64.9% by dry weight to 71.9% by dry weight of water. It may also optionally comprise at least one agent selected from a particle spacer, a dispersing agent, a steric stabilizing agent, an electrostatic stabilizing agent, 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.

[0099] The invention also provides a concentrated aqueous pigment paste comprising at least one composite C according to the invention and at least one organic or mineral colored pigment.

[0100] 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.

[0101] The invention very effectively enables 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.

[0102] 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.

[0103] The particular, advantageous or preferred characteristics of 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.

[0104] The various aspects of the invention can be illustrated by examples.

[0105] EXAMPLES

[0106] Preparation and characterization of Cl to C3 composites according to the invention

[0107] For the preparation of PI to P3 polymers according to the invention, the following compounds are used:

[0108] - compound al-1: isophorone diisocyanate (IPDI),

[0109] - compound bl: polyethylene glycol with a molecular mass of 10000 g / mol,

[0110] - 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 ethoxylated group 2.6 times on average,

[0111] - compound c3: monoalcohol of formula I in which R represents a cardanyl group ethoxylated 4 times.

[0112] Preparation and characterization of the Cl composite according to the invention

[0113] 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 ("PolycatDBU" - 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.

[0114] 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, along with 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.

[0115] The PI polymer is cooled to 60°C and a surfactant compound Tl (10-fold ethoxylated Cs 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.

[0116] Preparation and characterization of the C2 composite according to the invention

[0117] 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 added, and the mixture is dried before the addition 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.

[0118] The P2 polymer is cooled to 60°C and a surfactant compound Tl (10-fold ethoxylated Cs 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, 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. Preparation and characterization of the C3 composite according to the invention

[0119] 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. Compound (c3) (27.73 g) is then added, and the mixture is dried before the addition 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 polymer P3 according to the invention.

[0120] The P3 polymer is cooled to 60°C and a surfactant compound T2 (5-fold ethoxylated 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 separator with suction 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.

[0121] Preparation and characterization of aqueous compositions according to the invention

[0122] In a beaker equipped with a magnetic stirrer, the Cl₂ compound (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 mixture is visually homogeneous.

[0123] 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 containing the C2 and C3 composites are visually homogeneous after less than 30 minutes.

Claims

DEMANDS 1. 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: HO-R in which R independently represents a group chosen from a linear C1-C4o-alkyl group, a branched C3-C4o-alkyl group, a C5-C4o-cycloalkyl group, a linear C3-C4o-alkylene group, a branched C3-C4o-alkylene group, a C5-C4o-aryl group and their combinations, B- by grinding the mixture of compound T and polymer P.

2. Composite C according to claim 1, wherein: * 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 lower than the polymerization reaction temperature; more preferably at: - a temperature ranging from 45°C to 85°C or from 50°C to 65°C; or for which: * mixture A is prepared using a stirrer, or * the mixture is homogeneous, preferably monophasic, preferably monophasic upon direct visual examination; or for which: * 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 amount 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 whose median volume diameter, measured by sieving or dry laser granulometry, ranges from 0.3 mm to 8 mm or from 0.5 mm to 5 mm, preferably from 0.5 mm to 3 mm; or * comprising, relative to the total weight 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; preferably from 5% to 35% by weight of compound T and from 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 isothiazolone derivative, particularly of 5-chloro-2-methyl-2H-isothiazol-3-one (CMIT), 2-methyl-2H-isothiazol-3-one (MIT) and combinations thereof; or * not including any biocidal agent, preferably no derivative with an isothiazolone group, in particular of CMIT or MIT or their combinations.

4. Composite C according to 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 Cô-Ciô-alkyl-polyethylene glycol and Cô-Ciô-alkyl-polypropylene glycol; or wherein compound T is liquid at 30°C.

5. Composite C according to one of claims 1 to 4, wherein: * The diisocyanate compound (al) is 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); - 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 their combinations; more preferably, compound (al) is selected from IPDI, HDI, H12MDI and their combinations; 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 l,r,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) (H12MDI); * symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI); * asymmetrical 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) (H12MDI); * symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI); * asymmetrical 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, l,r,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; or * The polyhydroxylated compound (b) is a compound of formula II: HO-L n -OH Q in which: - L independently represents an oxyalkylene residue and n independently represents a number from 1 to 500; preferably wherein: - 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, 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 chosen from a linear Ci-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 their combinations; or - R independently represents a group chosen from a linear Ci-C24-alkyl group or a linear C3-C24-alkylene group, preferably a linear C4-C2o-alkyl group or a linear C4-C2o-alkylene group, more preferably a linear Cô-Cis-alkyl group or a linear Cô-Cis-alkylene group, much more preferably a linear Cô-Ciô-alkyl group or a linear Cô-Ciô-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 compound (b); or * The polymerization reaction involves: - from 10 mol% to 79.9 mol% or from 10 mol% to 74.5 mol%, preferably from 10 mol% to 68 mol% or from 10 mol% to 60 mol%, of monomer (a) or - 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), compared to the total molar quantity of monomers (a), (b) and (c).

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 10000 g / mol, preferably greater than 20000 g / mol or 30000 g / mol, or an average molar mass Mw less than 500000 g / mol, preferably less than 300000 g / mol or 200000 g / mol; or for which: * 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 for preparing a composite C according to any one of claims 1 to 7 comprising: A- a 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), - of at least one polyhydroxylated compound (b), - of at least one compound (c) of formula I: HO-R (I) in which R independently represents a group chosen from a linear C1-C4o-alkyl group, a branched C3-C4o-alkyl group, a C5-C4o-cycloalkyl group, a linear C3-C4o-alkylene group, a branched C3-C4o-alkylene group, a C5-C4o-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 ink composition, varnish composition, adhesive composition, paint composition, for example decorative paint or industrial paint, comprising: * at least one composite C according to one of claims 1 to 7, * at least one binding agent B, and possibly * 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.

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 chosen 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 claim 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 binding agent B, - from 3% by dry weight to 15% by dry weight of pigment Q and - from 64.9% dry weight to 71.9% dry weight water; and possibly 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 organic or mineral colored 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.

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