URETHANE CYCLOALKYL COPOLYMER THICKENER

Abstract

The invention relates to a thickening urethane copolymer prepared using cyclohexanol substituted with a linear or branched C4-C24-alkyl group or with a linear or branched C4-C24-alkylene group. The method for preparing this copolymer and its use in aqueous compositions, particularly in coating compositions, also form part of the invention.

Description

Title of the invention: CY-CLOALKYL URETHANE COPOLYMER THICKENING

[0001] The invention relates to a thickening urethane copolymer prepared using cyclohexanol substituted with a linear or branched C4-C24-alkyl group or with a linear or branched C4-C24-alkylene group. The method for preparing this copolymer and its use in aqueous compositions, particularly in coating compositions, also form part of the invention.

[0002] Many technical fields require the use of aqueous compositions. In particular, aqueous compositions of hydraulic binders, aqueous adhesives, aqueous detergents, aqueous cosmetics, aqueous inks, aqueous paper coatings, aqueous coatings, including aqueous varnishes, and aqueous paints, such as aqueous decorative paints or aqueous industrial paints, 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. 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 during storage, which can also manifest as viscosity variations. Such variations or degradations are particularly detrimental or damaging to aqueous hydraulic binder compositions, aqueous adhesive compositions, aqueous detergent compositions, aqueous cosmetic compositions, aqueous ink compositions, aqueous paper coating compositions, aqueous coating compositions, and especially aqueous varnish or paint compositions.

[0003] There is therefore a need to be able to have aqueous compositions which do not present such disadvantages or aqueous compositions which do not lead to such problems.

[0004] In particular, it is especially useful to have aqueous coating compositions, particularly aqueous varnish or paint compositions, whose viscosity is adapted to maintain their homogeneity as well as the integrity of their functional properties. Maintaining viscosity and limiting viscosity loss in these aqueous compositions should be possible over wide shear rate ranges.

[0005] Consequently, many aqueous coating compositions utilize rheology-modifying polymers. These polymers should enable aqueous compositions to achieve the desired rheological properties over a wide range of shear rates. These polymers should also improve the shear-thinning of these aqueous compositions by providing sufficient pseudoplasticity, 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 considered. In particular, it is important that the thickening copolymer and the pigments and binders used are compatible.

[0006] Furthermore, it is also important to improve the pigment compatibility of aqueous coating compositions, particularly paint compositions, especially with regard to the addition of pigment concentrates used for coloring. Without good pigment compatibility, the rheology of the composition can be severely degraded. Insufficient pigment compatibility can also lead to a decrease in color strength and result in an uneven or washed-out shade, potentially requiring the use of a larger quantity of pigment or causing aesthetic defects in the final coating.

[0007] Polymers known as thickening agents do not always provide a satisfactory solution to these various problems. Therefore, there is a need for improved rheology-modifying copolymers. The copolymer according to the invention provides a solution to all or part of the problems of prior art polymers.

[0008] Thus, the invention provides a copolymer P prepared by at least one polymerization reaction:

[0009] • of at least one isocyanate compound (a) chosen independently 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] R -C gH w -Qm - OH in which:

[0010] - R independently represents a grouping 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 their combinations;

[0011] - m independently represents 0 or a number from 1 to 100;

[0012] - Q represents a group selected from an oxyethylene group, a oxypropylene group, an oxybutylene group and their combinations.

[0013] Preferably for the copolymer P according to the invention, the isocyanate compound (a) is a diisocyanate compound (al) selected from:

[0014] - symmetrical aromatic diisocyanate compounds, preferably:

[0015] • diphenylmethylene 2,2'-diisocyanate (2,2'-MDI) and di-4,4'-diisocyanate phenylmethylene (4,4'-MDI); • 4,4'-dibenzyl diisocyanate (4,4'-DBDI); • Toluene 2,6-diisocyanate (2,6-TDI); • m-xylylene diisocyanate (m-XDI);

[0016] - symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (H[2MDI);

[0017] - symmetrical aliphatic diisocyanate compounds, preferably diisocyanate hexamethylene (HDI), pentamethylene diisocyanate (PDI);

[0018] - dissymmetric aromatic diisocyanate compounds, preferably:

[0019] • 2,4'-diphenylmethylene diisocyanate (2,4'-MDI); • 2,4'-dibenzyl diisocyanate (2,4'-DBDI); • toluene 2,4-diisocyanate (2,4-TDI);

[0020] - dissymmetric alicyclic diisocyanate compounds, preferably diisocyanate of isophorone (IPDI).

[0021] More preferably according to the invention, the compound (al) is chosen from IPDI, HDI, Hi2MDI and their combinations.

[0022] Also preferably for the copolymer P according to the invention, the isocyanate compound (a) may be 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. 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.

[0023] Also preferably, the polyisocyanate compound (a2) is chosen from:

[0024] - triphenylmethane-4,4',4”-triisocyanate or l,r,l”-methylidynetris (4-isocyanatobenzene);

[0025] - an isocyanurate compound, in particular an isocyanurate compound of a compound chosen from:

[0026] • symmetrical aromatic diisocyanate compounds, preferably:

[0027] • 2,2'-diisocyanate of diphenylmethylene (2,2'-MDI) and 4,4'-diisocyanate of di- phenylmethylene (4,4'-MDI); • 4,4'-dibenzyl diisocyanate (4,4'-DBDI); • Toluene 2,6-diisocyanate (2,6-TDI); • m-xylylene diisocyanate (m-XDI);

[0028] • 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:

[0029] • 2,4'-diphenylmethylene diisocyanate (2,4'-MDI); • 2,4'-dibenzyl diisocyanate (2,4'-DBDI); • toluene 2,4-diisocyanate (2,4-TDI);

[0030] - a biurea trimer compound, in particular a biurea trimer compound of a composed chosen from:

[0031] • symmetrical aromatic diisocyanate compounds, preferably:

[0032] • diphenylmethylene 2,2'-diisocyanate (2,2'-MDI) and di 4,4'-diisocyanate phenylmethylene (4,4'-MDI); • 4,4'-dibenzyl diisocyanate (4,4'-DBDI); • Toluene 2,6-diisocyanate (2,6-TDI); • m-xylylene diisocyanate (m-XDI);

[0033] • 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:

[0034] • 2,4'-diphenylmethylene diisocyanate (2,4'-MDI); • 2,4'-dibenzyl diisocyanate (2,4'-DBDI); • toluene 2,4-diisocyanate (2,4-TDI);

[0035] • dissymmetric alicyclic diisocyanate compounds, preferably isophorone diisocyanate (IPDI).

[0036] More preferably, compound (a2) is selected from triphenylmethane-4,4',4”-triisocyanate, 1,1',1”-methylidynetris (4-isocyanatobenzene), an isocyanurate of HDI, an isocyanurate of IPDI, an isocyanurate of PDI, a trimer of HDI biurea and a trimer of IPDI biurea, a trimer of PDI biurea.

[0037] Preferably for the copolymer P according to the invention, the poly-hydroxylated compound (b) is a compound (bl) of formula II: [Chem II] HO-U-QH in which: - L independently represents an oxyalkylene residue;

[0038] - n independently represents a number from 30 to 1000.

[0039] Preferably for the copolymer P according to the invention, the poly-hydroxylated compound (b) is a compound (bl) of formula II in which: - L independently represents an oxyethylene residue; or

[0040] - n independently represents a number from 50 to 400, preferably from 100 to 300.

[0041] More preferably for the copolymer P according to the invention, the poly-hydroxylated compound (b) is a compound (bl) of formula II in which L independently represents an oxyethylene residue and p independently represents a number from 50 to 400, preferably from 100 to 300.

[0042] According to the invention, compound (bl) of formula II can be associated with a non-alkoxylated compound (b2) comprising at least three hydroxyl groups. Preferably according to the invention, compound (b2) comprises three hydroxyl groups. Even more preferably, it is selected from glycerol, pentaerythritol, and combinations thereof.

[0043] 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, compound (b3) is different from compound (b2) and comprises three hydroxyl groups. Even more preferably, it is polyethoxylated glycerol.

[0044] Advantageously according to the invention, the copolymer P can be prepared using one or more combinations of the compounds (bl), (b2) and (b3).

[0045] 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 12,000 g / mol. According to the invention, the molar mass of compounds (b), (bl), or (b3) is

[0046] determined by Size Exclusion Chromatography (SES) or in English "Gel Permeation Chromatography" (GPC). This technique uses an apparatus A Waters brand liquid chromatography system equipped with a detector. This detector is a Waters 2414 type refractometric concentration detector. This liquid chromatography system has two size-exclusion columns to separate the different molecular weights of the polymers or compounds being studied. The elution liquid phase is an organic phase composed of THF (HPLC grade, unstabilized). In the first step, approximately 25 mg of the compound is solubilized in 5 mL of THF, to which 0.1 mol% water is added as an internal flow marker. The solution is then filtered to 0.2 µm. 50 pL is then injected into the chromatography system (eluent: THF, HPLC grade, unstabilized). The liquid chromatography system contains an isocratic pump (Waters 515) with a flow rate set at 0.3 mL / min.The chromatography apparatus also includes a furnace with a series column system: a 250 mm long, 4.6 mm diameter Agilent PLgel MiniMIX-A column followed by a 250 mm long, 4.6 mm diameter Agilent PLgel MiniMIX-B column. The detection system consists of a Waters 2414 RI refractometer. The columns are maintained at 35°C and the refractometer is also heated to 35°C. The chromatography apparatus is calibrated using polymethyl methacrylate standards certified by the supplier Agilent (EasiVial PMMA).

[0047] Preferably according to the invention, compound (c) is a compound of formula I in which R independently represents a group selected 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 Ci2-Ci8-alkyl group or a linear Ci2-Ci8-alkylene group, much more preferably a linear Ci5-alkyl group.

[0048] 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 may be present within the alkylene chain.

[0049] Preferably according to the invention, the compound (c) is a compound of formula I in which m independently represents 0 or a number from 2 to 50 or from 2 to 20 or from 2 to 10.

[0050] 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 and oxypropylene groups, preferably in a molar proportion (oxyethylene groups / oxypropylene groups) of from 95 / 5 to 50 / 50, preferably ranging from 80 / 50 to 70 / 30 or from 65 / 35 to 55 / 45.

[0051] More preferably according to the invention, compound (c) is a compound of formula I in which:

[0052] - R independently represents a grouping chosen from a C4-C24 grouping - linear alkyl 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 Ci2-Ci8-alkyl group, a linear Ci2-Ci8-alkylene group, much more preferably a linear Ci5-alkyl group,

[0053] - m independently represents 0 or a number from 2 to 50 or from 2 to 20 or again from 2 to 10; and

[0054] - Q represents an oxyethylene group or a combination of groups oxyethylenes 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.

[0055] In a much more preferred manner according to the invention, compound (c) is a compound of formula I in which:

[0056] - R independently represents a grouping chosen from a C4-C24 grouping - linear alkyl, preferably a linear C6-C20-alkyl group, more preferably a linear Ci2-Ci8-alkyl group, much more preferably a linear Ci5-alkyl group,

[0057] - m independently represents 0 or a number from 2 to 50 or from 2 to 20 or again from 2 to 10; and

[0058] - Q represents an oxyethylene group or a combination of groups oxyethylenes 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.

[0059] Preferably according to the invention, compound (c) is a compound of formula I in which R independently represents a linear alkyl group.

[0060] For the preparation of copolymer P according to the invention, the quantities of compounds (a), (b), and (c) may vary. Preferably for copolymer P, 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), compared to the total molar quantity of monomers (a), (b) and (c).

[0061] In a much more preferred manner according to the invention, the polymerization reaction can involve: - from 10 to 79.9 mol% or from 10 to 74.5 mol% of monomer (a), - from 20 to 89.9 mol% or from 25 to 89.5 mol% of monomer (b), and - from 0.1 to 70 mol% or from 0.5 to 65 mol% of monomer (c),

[0062] with respect to the total molar quantity of monomers (a), (b) and (c).

[0063] Even more preferably according to the invention, the polymerization reaction can implement : - 10 to 68% molar or 10 to 60% molar, of monomer (a), - 30 to 88% molar or 35 to 85% molar, of monomer (b), and - 2 to 60% molar or 5 to 55% molar, of monomer (c),

[0064] with respect to the total molar quantity of monomers (a), (b) and (c).

[0065] According to the invention, the polymerization reaction may involve only compounds (a), (b), and (c), or it may involve one or more additional compounds. In this case, the polymerization reaction may also involve at least one hydrophobic compound (d) different from compound (c), preferably chosen from a compound of formula (III): [Chem III] R1 -(OE)q-(OP)r-OH in which: - q and r, whether 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 CH2 CH(CH3)O, - R1 independently represents a C4-C4o-alkyl group, linear or branched, preferably a C6-C30-alkyl group, linear or branched, more preferably a C6-C22-alkyl group, linear or branched.

[0066] 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 amount of compounds involved.

[0067] 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 various compositions. Thus, the invention provides a rheology control composition comprising at least one copolymer P according to the invention. The composition The rheological control according to the invention can be treated with acid leading to a pH below 8, preferably above 6. This treatment can be carried out using an acid, in particular a carboxylic acid such as acetic acid or lactic acid.

[0068] The rheological control composition according to the invention may also include at least one solvent, in particular water or a coalescing solvent, for example glycol, butyl glycol, butyldiglycol, monopropylene glycol, ethylene glycol, ethylenediglycol, "Dowanol" products (CAS number 34590-94-8), "Texanol" products (CAS number 25265-77-4); or combined with at least one additive selected from an amphiphilic compound, in particular a surfactant compound, preferably a hydroxylated surfactant compound, for example alkyl-polyalkyleneglycol, in particular alkyl-polyethylene glycol and alkyl-polypropyleneglycol; a polysaccharide derivative, for example cyclodextrin, cyclodextrin derivative, polyethers, alkyl-glucosides; a hydrotropic compound, an antifoaming agent, a biocidal agent and combinations thereof.

[0069] The rheological control composition according to the invention is particularly suitable for facilitating the use of pigments in aqueous media, especially organic or mineral pigments. It can be incorporated into a specific pigment formulation. Thus, the invention provides an aqueous formulation comprising: - at least one rheological control composition according to the invention; possibly - at least one organic or mineral pigment or organic, organometallic or mineral particles, for example calcium carbonate, talc, kaolin, mica, silicates, silica, metal oxides, in particular titanium dioxide, iron oxides; and possibly - 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.

[0070] 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.

[0071] The copolymer P according to the invention can also be used in the field of printing, particularly 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.

[0072] The invention also provides a method for controlling the viscosity of an aqueous composition that includes the addition of at least one copolymer P according to the invention to that composition. The viscosity control method according to the invention is implemented for an aqueous composition that is an aqueous formulation according to the invention.

[0073] 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.

[0074] The following examples illustrate the different aspects of the invention.

[0075] Examples:

[0076] Example 1: Preparation of copolymers P according to the invention

[0077] PI copolymer according to the invention:

[0078] In a 2 L glass reactor equipped with mechanical stirring, a vacuum pump, a nitrogen inlet, and heated by means of a double jacket through which oil circulates, a compound (b) (polyethylene glycol - molecular mass 10,000 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, followed by a compound (c1) (hydrogenated cardanol, of formula I in which R represents a linear Ci5-alkyl group and m represents O) (7.7 g) and dodecanol (4.6 g) are added over 10 min. Then, a diisocyanate compound (al) (isophorone diisocyanate, IPDI) (11 g) is introduced using a syringe and under stirring at 150 rpm. The reaction is continued at 100°C for 1 hour.

[0079] Next, the isocyanate concentration is verified by back titration. One gram of the reaction mixture is taken, and an excess of dibutylamine (e.g., 1 molar) is added. This dibutylamine reacts with any isocyanate groups potentially present in the mixture. Any unreacted dibutylamine is then titrated with hydrochloric acid (e.g., 1 N). The amount of isocyanate groups present in the reaction mixture can then be deduced. If this amount is not zero, the reaction is continued in 15-minute increments until the reaction is complete. The resulting PI copolymer is formulated using ethoxylated alcohol-type 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 antifoaming 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, and 9.5% by mass of surfactant compounds. active ingredients and 73% water mass.

[0080] P2 copolymer according to the invention:

[0081] In a 2 L glass reactor equipped with mechanical stirring, a vacuum pump, a nitrogen inlet, and heated by means of a double jacket through 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, followed by a compound (c1) (hydrogenated cardanol) (7.7 g), dodecanol (3.4 g), and octan-l-ol (0.6 g) over 15 min. Finally, a diisocyanate compound (a1) (isophorone diisocyanate, IPDI) (10.8 g) is introduced using a syringe and under stirring at 150 rpm. The reaction is continued at 100°C for 1 hour.

[0082] Then, the isocyanate content is verified to be zero by back titration. The resulting P2 copolymer is formulated using ethoxylated alcohol-type surfactants (“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 antifoaming agent (“Tego” 1488 “Evonik”), and water (725 g). A rheological control aqueous composition is obtained, consisting of 17.5% by mass of the P2 copolymer according to the invention, 9.5% by mass of surfactants, and 73% by mass of water.

[0083] Example 2: Preparation and characterization of an aqueous paint formulation according to the invention:

[0084] By mixing the various ingredients under stirring, a matte paint formulation Fl is prepared according to the invention. The compounds and quantities (g) used are detailed in Table 1.

[0085] [Tables 1] Ingredients of the matte paint formulation Quantity (g) “Ecodis” P50 (dispersant “Coatex”) 0.4 “Tego” 825 (anti-foam “Tego”) 0.1 “Acticide” MBS (bactericide “Thor”) 0.2 “Tiona” 568 (TiO2 “Tronox”) 8.1 “Omyacoat” 850 OG (CaCO3 “Omya”) 13.1 “Durcal” 2 AV (CaCO3 “Omya”) 30.3 “Mowilith” LDM 1871 (Binder “Celanese”) 15.1 NaOH (20% in water) 0.1 Aqueous composition of PI copolymer 2.2 Water 30.4 Total 100.00

[0086] Then, the Fl paint formulation is colored by adding 5% by weight of a black pigment (“Colanyl” N500 black “Clariant”) to obtain the colored Fl formulation according to the invention.

[0087] Then, for the colored Fl formulation, measurements are taken at 25°C:

[0088] • Brookfield viscosity at 10 rpm (pBlO, rnPa.s); • Brookfield viscosity at 100 rpm (pBlOO, rnPa.s); • the Plane Cone viscosity or ICI viscosity measured at high velocity gradient (pi, rnPa.s); • Stormer viscosity measured using the standard modulus, at medium velocity gradient (pS, Krebs Units or KU).

[0089] 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.

[0090] The pigment compatibility of the Fl formulation is evaluated on a dry paint film. The test, known as the finger rub test, of colored paint applied at a wet thickness of 150 micrometers on a contrast card (smear rub test) allows a small portion of the surface of the freshly applied colored paint film to be subjected to a shear effect generated by a circular finger movement. The shear effect can modify the stability and distribution of the colored pigment within the matrix of the colored paint film and, consequently, the intensity of the color at the sheared area.

[0091] Once the colored paint film is dry, the color difference between the area of ​​the film The initially sheared colored paint area and the unsheared colored paint area are measured using a spectro-guide sphere gloss type spectrophotometer marketed by the company "Byk".

[0092] The color difference is quantified by the AE value calculated from the measurement parameters corresponding to the known chromatic space L*a*b*. A low AE value means a reduced color difference between the sheared and unsheared areas, and therefore improved pigment compatibility.

[0093] The unsheared colored paint area is also measured according to one of the parameters of the L*a*b* color space. The L* parameter quantifies the intensity of the color. A low value for the L* parameter indicates 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 used. The results are presented in Table 2.

[0094] [Tables2] Viscosity (mPa.s) Formulation Colored Fl pBlO T=0 12,560 pBlOO 2,536 pS 10³ ft 90 pBlO T=24H 12,240 pBlOO 2,600 pS 10⁴ ft 80 Pigment compatibility AE 0.21 L* 30.15

[0095] For the colored Fl formulation according to the invention, the copolymer according to the invention allows for precise control of the various viscosity components, both after preparation and over time. The copolymer according to the invention provides good pigment compatibility for this paint formulation.

Claims

Demands

1. Copolymer P prepared by at least one polymerization reaction: • of at least one isocyanate compound (a) chosen independently 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: R-CsHi0-Qm-OH in which: - R independently represents a group in position 3 of the ring 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 their combinations; - 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 wherein the isocyanate compound (a) is: • a diisocyanate compound (al) 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); - asymmetrical aromatic dusocyanate 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 dusocyanate compounds, preferably isophorone diisocyanate (IPDI), Preferably, the compound (al) is chosen from IPDI, HDI, H 12MDI and their combinations; or • a polyisocyanate compound (a2) comprising strictly more than 2 isocyanate functions or more than 2.2 isocyanate functions or 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) 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 dusocyanate 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 düsocyanate (m-XDI); • symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (Hi2MDI); • symmetrical aliphatic diisocyanate compounds, preferably hexamethylene düsocyanate (HDI), pentamethylene düsocyanate (PDI); • dissymmetric aromatic diisocyanate compounds, preferably: • 2,4'-diphenylmethylene diisocyanate (2,4'-MDI); • 2,4'-dibenzyl düsocyanate (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 düsocyanate (4,4'-DBDI); • Toluene 2,6-diisocyanate (2,6-TDI); • m-xylylene düsocyanate (m-XDI); • symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (Hi2MDI); • symmetrical aliphatic diisocyanate compounds, preferably hexamethylene düsocyanate (HDI), pentamethylene düsocyanate (PDI); • dissymmetric aromatic diisocyanate compounds, preferably: • 2,4'-diphenylmethylene diisocyanate (2,4'-MDI); • 2,4'-dibenzyl diisocyanate (2,4'-DBDI); • 2,4-toluene diisocyanate (2,4-TDI); • asymmetric alicyclic diisocyanate compounds, preferably isophorone diisocyanate (IPDI), preferably 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.

3. Copolymer P according to any one of claims 1 or 2 wherein the polyhydroxylated compound (b) is selected from: • a compound (b 1) of formula II: [Chem II] HO-U-OH in which: - L independently represents an oxyalkylene residue; - n independently represents a number from 30 to 1000; • a compound (b 1) 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 any one of claims 1 to 3 wherein compound (b) is selected from: • a compound (bl) of formula II in which: - L independently represents an oxyethylene residue; or - n independently represents a number from 50 to 400, preferably from 100 to 300; or - L independently represents an oxyethylene residue and p independently represents a number from 50 to 400, preferably from 100 to 300; • a compound (b2) comprising three hydroxyl groups, preferably selected 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 any one of claims 1 to 4 wherein 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 any one of claims 1 to 5 wherein compound (c) is a compound of formula I in which: - R independently represents a group selected 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 Ci2-Ci8-alkyl group or a linear Ci2-Ci8-alkylene group, much more preferably a linear Ci5-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 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 any one of claims 1 to 6 wherein the polymerization reaction involves: - 10 to 79.9 mol% or 10 to 74.5 mol%, preferably 10 to 68 mol% or 10 to 60 mol%, of monomer (a) or - 20 to 89.9 mol% or 25 to 89.5 mol%, preferably 30 to 88 mol% or 35 to 85 mol%, of monomer (b), or - 0.1 to 70 mol% or 0.5 to 65 mol%, preferably 2 to 60 mol% or 5 to 55 mol%, of monomer (c), relative to the total molar amount of monomers (a), (b) and (c).

8. Copolymer P according to any one of claims 1 to 7, wherein the polymerization reaction also involves at least one hydrophobic compound (d) different from compound (c), preferably selected from a compound of formula (III): [Chem III] R1-(OE)tî-(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 selected from CH(CH3)CH2O and CH2CH(CH3)O, - R1 independently represents a C4-C40-alkyl group, linear or branched, preferably a C6-C30-alkyl group, linear or branched, more preferably a C6-C22-alkyl group, linear or branched, preferably less than 60 mol%, preferably from 0.05 to 60% molar, in particular from 0.1 to 60% molar, more preferably less than 50% molar, preferably from 0.05 to 50% molar,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 any one of claims 1 to 8, optionally acid-treated leading to a pH below 8, preferably above 6, for example by means of an acid, in particular a carboxylic acid such as acetic acid or lactic acid.

10. Rheological control composition according to claim 9 also comprising at least one solvent, in particular water or a coalescing solvent, for example glycol, butyl glycol, butyldiglycol, monopropylene glycol, ethylene glycol, ethylenediglycol, "Dowanol" products of which CAS number 34590-94-8, "Texanol" products whose CAS number is 25265-77-4; or combined with at least one additive selected from an amphiphilic compound, including a surfactant compound, preferably a hydroxylated surfactant compound, for example alkyl-polyalkyleneglycol, including alkyl-polyethyleneglycol and alkyl-polypropyleneglycol; a polysaccharide derivative, for example cyclo-dextrin, cyclodextrin derivative, polyethers, alkyl-glucosides; a hydrotropic compound, an antifoaming agent, a biocidal agent and combinations thereof.

11. Aqueous formulation comprising: - at least one composition according to any one of claims 9 or 10; optionally - at least one organic or mineral pigment or organic, organometallic 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, 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.

12. Formulation according to claim 11 of coating, in particular an ink formulation, a varnish formulation, an adhesive formulation, a paint formulation, for example decorative paint or industrial paint.

13. Concentrated aqueous pigment paste comprising at least one copolymer P according to any one of claims 1 to 8 and at least one organic or mineral colour pigment.

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

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