ALKYL URETHANE COPOLYMER THICKENING

Abstract

The invention relates to a thickening urethane copolymer prepared using a polyalkoxylated Guerbet alcohol comprising a doubly branched alkyl group. The method for preparing this copolymer and its use in aqueous compositions, particularly in coating compositions, are also part of the invention.

Description

Title of the invention: Thickening Alkyl Urethane Copolymer

[0001] The invention relates to a thickening urethane copolymer prepared using a polyalkoxylated Guerbet alcohol comprising a doubly branched alkyl 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 gradient 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: * 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) obtained by: - dimerization of two identical or different compounds of formula I: [Chem I] R-CH[(CH2)mCH3]-(CH2)n-OH (I) in which: ** R independently represents a linear C4-C9-alkyl group; ** m represents independently 0 or 1; ** n independently represents a number from 2 to 7; and - polyalkoxylation of the dimer obtained.

[0009] Preferably for the copolymer P according to the invention, 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); - 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).

[0010] Preferably according to the invention, the compound (al) is chosen from IPDI, HDI, Hi2MDI and their combinations.

[0011] 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.

[0012] Also preferably, the polyisocyanate compound (a2) is chosen from: ** triphenylmethane-4,4',4”-triisocyanate or l,l',l”-methylidynetris (4-isocyanatobenzene); * an isocyanurate compound, in particular an isocyanurate compound of a compound chosen from: - symmetrical aromatic diisocyanate compounds, preferably: ** 2,2'-diphenylmethylene diisocyanate (2,2'-MDI) and 4,4'-diphenylmethylene diisocyanate (4,4'-MDI); **4,4'-dibenzyl diisocyanate (4,4'-DBDI); **Toluene 2,6-diisocyanate (2,6-TDI); ** m-xylylene diisocyanate (m-XDI); - symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (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); * 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); - 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), preferably 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.

[0013] Preferably for the copolymer P according to the invention, the poly-hydroxylated compound (b) is a compound (bl) of formula II: [Chem II] HO-LP-OH (II) in which: - L independently represents an oxyalkylene residue; - p independently represents a number from 30 to 1000.

[0014] 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 - p independently represents a number from 50 to 400, preferably from 100 to 300.

[0015] 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.

[0016] 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.

[0017] 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.

[0018] Advantageously according to the invention, the copolymer P can be prepared using one or more combinations of the compounds (bl), (b2) and (b3).

[0019] 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 determined by Size Exclusion Chromatography (CES), also known as Gel Permeation Chromatography (GPC). This technique uses a Waters liquid chromatography instrument equipped with a detector. This detector is a Waters 2414 type refractometric concentration detector. This liquid chromatography instrument is equipped with 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 a 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 apparatus (eluent: THF, HPLC grade, unstabilized). The liquid chromatography apparatus contains an isocratic pump (Waters 515) with a flow rate set at 0.3 mL / min. The chromatography apparatus also includes 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 type RI refractometric detector. The columns are maintained at a temperature of 35°C and the refractometer is brought to a temperature of 35°C.The chromatography apparatus is calibrated using polymethyl methacrylate standards certified by the supplier "Agilent" ("EasiVial" PMMA).

[0020] Essentially, according to the invention, compound (c) is obtained by a dimerization reaction of two compounds of formula I. This dimerization is a Guerbet reaction carried out with these two alcohols of formula I. The dimerization reaction and its implementation conditions are known as such. Compound (c) can be prepared from a single compound of formula I or from two different compounds of formula I. The resulting dimer is treated to obtain the polyalkoxylated compound (c).

[0021] Preferably according to the invention, the dimerization of two identical compounds of formula I leads to a homodimer (cl). Also preferably according to the invention, compound (c) is a homodimer (cl) obtained by dimerization of two identical compounds of formula I in which: - R represents a linear C5-C7-alkyl group; - m represents 0 or 1, preferably 0; - n represents a number from 2 to 7.

[0022] More preferably according to the invention, compound (c) is a homodimer (cl) obtained by dimerization of two identical compounds of formula I in which: - R represents a linear C4-C9-alkyl group, preferably a linear C5-C7-alkyl group; - m represents 0 or 1, preferably 0; - n represents a number from 5 to 7, preferably from 4 to 6, more preferably 4 or 5.

[0023] In a particularly preferred manner according to the invention, the dimerization is carried out starting from two different compounds of formula I and leads to a mixture comprising two different homodimers (cl) and one heterodimer (c2). Preferably, this is of a mixture consisting of two different homodimers (cl) and one heterodimer (c2). Also preferably, a mixture of compounds (c) can be obtained by dimerization of two different compounds of formula I in which: - R independently represents a linear C5-C7-alkyl group; - m represents independently 0 or 1, preferably 0; - n independently represents a number from 2 to 7.

[0024] Preferably according to the invention, a mixture of compounds (c) can be obtained by dimerization of two different compounds of formula I in which: - R independently represents a linear C4-C9-alkyl group, preferably a linear C5-C7-alkyl group; - m represents independently 0 or 1, preferably 0; - n independently represents a number from 5 to 7, preferably from 4 to 6, more preferably 4 or 5.

[0025] A preferred mixture of compounds (c) comprises a heterodimeric compound (c2) obtained by dimerization of a first compound of formula I in which R represents a linear C5-alkyl group, m represents 0 and n represents 5 and of a second different compound of formula I in which R represents a linear C7-alkyl group, m represents 0 and n represents 4.

[0026] A particularly preferred mixture of compounds (c) comprises: ** a heterodimeric compound (c2) obtained by dimerization of a first compound of formula I in which R represents a linear C5-alkyl group, m represents 0 and n represents 5 and of a second different compound of formula I in which R represents a linear C7-alkyl group, m represents 0 and n represents 4, ** a first homodimer (cl) obtained by dimerization of a compound of formula I in which R represents a linear C5-alkyl group, m represents 0 and n represents 5, ** a second homodimer (cl) obtained by dimerization of a different compound of formula I in which R represents a linear C7-alkyl group, m represents 0 and n represents 4.

[0027] According to the invention, dimerization carried out from two different formula I compounds can lead to a mixture consisting of 2 different homodimers (cl) and one heterodimer (c2).

[0028] According to the invention, compound (c) is prepared by dimerization of two compounds of formula I and polyalkoxylation of the resulting dimer. The polyalkoxylation reaction and its implementation conditions are known as such. Preferably for the copolymer P according to the invention, compound (c) comprises from 10 to 150 alkoxylations. More preferably, compound (c) comprises from 20 to 100 alkoxylations or from 10 to 70 alkoxylations, more preferably from 20 to 60 alkoxylations. Also preferred, compound (c) is polyethoxylated or is polyethoxylated-polypropoxylated or is polyethoxylated-polybutoxylated; preferably, compound (c) is polyethoxylated. More preferably, compound (c) is polyethoxylated. Particularly preferred, compound (c) comprises from 10 to 150 ethoxylations, more preferably from 20 to 100 ethoxylations or from 10 to 70 ethoxylations, much more preferably from 20 to 60 ethoxylations.

[0029] 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 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 (a) or - 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 (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).

[0030] Also preferably according to the invention, the polymerization reaction can involve: - 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 (a), - 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 (b), and - from 0.1 to 70 mol% or from 0.5 to 65 mol%, preferably from 2 to 60 mol% or from 5 to 55 mol%, of monomer (c), relative to the total molar amount of monomers (a), (b) and (c).

[0031] 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 (III) in which: - q and r, whether identical or different, independently represent 0 or an integer or decimal number less than 150, q or r is not equal to 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 C6-C40-alkyl group, linear or branched, a phenyl group, a polyphenyl group, preferably a Cio-C3o-alkyl group, linear or branched, more preferably a Ci2-C22-alkyl group, linear or branched, or a group comprising 2 to 5 phenyls or a tristyrylphenyl group or a pentastyrylcumylphenyl group, preferably less than 20 mol%, preferably from 0.05 to 20 mol%, in particular from 0.1 to 10 mol%, of compound (d) relative to the total molar amount of compounds committed.

[0032] The copolymer P according to the invention can be used in many technical fields, particularly 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 rheology control composition according to the invention can be acid-treated 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.

[0033] 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 of which CAS number is 34590-94-8, "Texanol" products of which CAS number is 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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] The following examples illustrate the different aspects of the invention. Examples

[0040] Example 1: Preparation of PI and P2 copolymers according to the invention

[0041] In a 3 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) is introduced and heated to 95°C under vacuum. Under stirring and inert atmosphere, 200 ppm of a bismuth carboxylate type catalyst (K Kat B221) is added to the medium and then a compound (c) (prepared by Guerbet reaction dimerization of a compound of formula I in which R represents a linear C5-alkyl group, m represents 0 and n represents 5 and of a compound of formula I in which R represents a linear C7-alkyl group, m represents 0 and n represents 4, ethoxylated 50 times - "Isofol" 2426S-50OE) is added in 5 min. Then, a diisocyanate (al) compound (hexamethylene diisocyanate, HDI) is introduced using a syringe under agitation at 150 rpm.The reaction is continued for 60 minutes at 100°C ± 5°C.

[0042] Then, the isocyanate concentration is verified to be zero by back titration. 1 g of the reaction medium is to which an excess of dibutylamine (e.g., 1 molar) is added. This dibutylamine reacts with any isocyanate groups potentially present in the medium. Any unreacted dibutylamine is then titrated with hydrochloric acid (e.g., 1 N). The amount of isocyanate groups present in the reaction medium can then be deduced. If this amount is non-zero, the reaction is continued in 15-minute increments until it is complete. When the concentration reaches zero, the PI copolymer is obtained.

[0043] The PI copolymer comprising 46 mol% of compound a, 17 mol% of compound b and 37 mol% of compound c. It is formulated using an ethoxylated alcohol-type surfactant compound (“Emulan” HE 51 BASF), and 1000 ppm of a biocidal agent (Biopol SMV Chemipol), 1000 ppm of an antifoaming agent (Tego 1488 Evonik), and water. The resulting aqueous composition consists of 30% by mass of the PI copolymer according to the invention, 20% by mass of the surfactant compound, and 50% by mass of water. The quantities used are shown in Table 1.

[0044] [Tab 1] < opoiymer PI compound a (g) 8.5 compas. b tyj s 04 compound e (g) surfactant compound (HE51 ) (g) 201.8 Water 494.5

[0045] Example 2: preparation of a paint formulation according to the invention

[0046] By mixing the various ingredients under stirring, a matte paint formulation according to the invention is prepared. The compounds and quantities (g) used are detailed in Table 2.

[0047] [Tab 2] Ingredients of the matte paint formulation Quantity (g) “Ecodis” P50 (dispersant “Coatex”) 2.00 “Tego” 810 (antifoam “Tego”) 0.51 “Acticide” MBS (bactericide “Thor:”) 1.00 “Tiona” 568 (TiCh “Tronox”) 40.01 “Omyacoat” 850 OG (CaCO₃ “Omya”) 110.00 “Durcal” 2 AV (CaCO₃ “Omya”) 150.29 “Acronal” S790 (binder “Basf”) 65.00 Monopropylene glycol 5.06 “Texanol” (Coolescent “Eastman”) 5.02 NaOH (20% in water) 0.41 Aqueous composition of PI copolymer according to the invention 5.02 Water 115.68 Total 500.00

[0048] Then, the paint formulation is colored by adding 5% by weight of a black pigment (“Colanyl” N500 black “Clariant”) to obtain the Fl formulation according to the invention.

[0049] Then, for formulation Fl, measurements are taken at 25°C: * Brookfield viscosity at 10 rpm (pBlO, mPa.s); * Brookfield viscosity at 100 rpm (pBlOO, mPa.s); * Plane Cone viscosity or ICI viscosity measured at high velocity gradient (pi, mPa.s); * Stormer viscosity measured using the standard modulus, at medium velocity gradient (pS, Krebs Units or KU).

[0050] 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 3.

[0051] The pigment compatibility of the Fl formulation is evaluated on a dry paint film. The initially white paint is colored by adding 5% of a black pigment-based colorant (“Colanyl” N500 black “Clariant”), a percentage calculated relative to the weight of the white paint formulation.

[0052] The rub-out test, known as such, of colored paint applied at a wet thickness of 150 micrometers to a contrast card, allows a small portion of the surface of the freshly applied colored paint film to be subjected to a shearing effect generated by a circular motion of the finger. This shearing 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.

[0053] Once the colored paint film is dry, the color difference between the initially sheared area of ​​the colored paint film and the unsheared area of ​​colored paint is measured using a sphere gloss spectro-guide spectrophotometer marketed by the company "Byk".

[0054] 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.

[0055] 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 implemented. The results are presented in Table 3.

[0056] [Table 3]

[0057] For formulation Fl 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 to the 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) obtained by: - Dimerization of two identical or different compounds of formula I by a Guerbet reaction: [Chem I] R-CH[(CH2)mCH3]-(CH2)n-OH (I) in which: ** R independently represents a linear C4-C9-alkyl group; ** m represents independently 0 or 1; ** n independently represents a number from 2 to 7; and - polyalkoxylation of the resulting dimer.

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) (H[2MDI); - 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), Preferably, the compound (al) is chosen from IPDI, HDI, MDI 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 1,1',1"-methylidynetris (4-isocyanatobenzene); or *** 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); *** asymmetric aromatic diisocyanate compounds, preferably: ** 2,4'-diphenylmethylene diisocyanate (2,4'-MDI); ** 2,4'-dibenzyl diisocyanate (2,4'-DBDI); **Toluene 2,4-diisocyanate (2,4-TDI); ** 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); ** 2,6-toluene 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); *** unsymmetrical aromatic diisocyanate compounds, preferably: ** diphenylmethylene 2,4'-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 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.;

3. Copolymer P according to any one of claims 1 or 2 wherein the polyhydroxylated compound (b) is selected from: * a compound (bl) of formula II: [Chem II] HO-LP-OH (II) in which: - L independently represents an oxyalkylene residue; - p independently represents a number from 30 to 1000; * a compound (bl) of formula II associated with a non-alkoxylated compound (b2) comprising at least three hydroxyl groups; * a polyalkoxylated compound (b3) comprising at least three hydroxyl groups; * combinations thereof.

4. Copolymer P according to any one of claims 1 to 3 wherein the compound (b) is chosen from: * a compound (bl) of formula II in which: - L independently represents an oxyethylene residue; or - p 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 chosen from glycerol, pentaerythritol and their combinations; * polyethoxylated pentaerythritol or a compound (b3) different from compound (b2) and comprising three hydroxyl groups, preferably a compound (b3) which is polyethoxylated glycerol.

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: * the dimerization of two identical compounds of formula I leads to a homodimer (cl); or * compound (c) is a homodimer (cl) obtained by dimerization of two identical compounds of formula I in which: - R represents a linear C5-C7-alkyl group; - m represents 0 or 1, preferably 0; - n represents a number from 2 to 7; or * compound (c) is a homodimer (cl) obtained by dimerization of two identical compounds of formula I in which: - R represents a linear C4-C9-alkyl group, preferably a linear C5-C7-alkyl group; - m represents 0 or 1, preferably 0; - n represents a number from 5 to 7, preferably from 4 to 6, more preferably 4 or 5.

7. Copolymer P according to any one of claims 1 to 5 wherein: * the dimerization of two different compounds of formula I leads to a mixture comprising 2 different homodimers (cl) and one heterodimer

8. (c2); or * a mixture of compounds (c) is obtained by dimerization of two different compounds of formula I in which: - R independently represents a linear C5-C7-alkyl group; - m represents independently 0 or 1, preferably 0; - n independently represents a number from 2 to 7; or * a mixture of compounds (c) is obtained by dimerization of two different compounds of formula I in which: - R independently represents a linear C4-C9-alkyl group, preferably a linear C5-C7-alkyl group; - m represents independently 0 or 1, preferably 0; - n independently represents a number from 5 to 7, preferably from 4 to 6, more preferably 4 or 5; or * a mixture of compounds (c) comprises a heterodimeric compound (c2) obtained by dimerization of a first compound of formula I in which R represents a linear C5-alkyl group, m represents 0 and n represents 5 and a second different compound of formula I in which R represents a linear C7-alkyl group, m represents 0 and n represents 4; or * a mixture of compounds (c) comprises: ** a heterodimeric compound (c2) obtained by dimerization of a first compound of formula I in which R represents a linear C5-alkyl group, m represents 0 and n represents 5 and of a second different compound of formula I in which R represents a linear C7-alkyl group, m represents 0 and n represents 4, ** a first homodimer (cl) obtained by dimerization of a compound of formula I in which R represents a linear C5-alkyl group, m represents 0 and n represents 5, ** a second homodimer (cl) obtained by dimerization of a different compound of formula I in which R represents a linear C7-alkyl group, m represents 0 and n represents 4. Copolymer P according to any one of claims 1 to 7, wherein: * Compound (c) comprises from 10 to 150 alkoxylations, preferably from 20 to 100 alkoxylations, or from 10 to 70 alkoxylations, more preferably from 20 to 60 alkoxylations, or * compound (c) is polyethoxylated or is polyethoxylated-polypropoxylated or is polyethoxylated-polybutoxylated, preferably compound (c) is polyethoxylated, or * Compound (c) comprises from 10 to 150 ethoxylations, preferably from 20 to 100 ethoxylations or from 10 to 70 ethoxylations, more preferably from 20 to 60 ethoxylations.

9. Copolymer P according to any one of claims 1 to 8 wherein the polymerization reaction involves: - 20 to 89.9 mol% or 25 to 89.5 mol%, preferably 30 to 88 mol% or 35 to 85 mol%, of monomer (a) or - 10 to 79.9 mol% or 10 to 74.5 mol%, preferably 10 to 68 mol% or 10 to 60 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 mol% of monomers (a), (b) and (c).

10. Copolymer P according to any one of claims 1 to 9, 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] R*-(OE)q-(OP)r-OH (III) wherein: - q and r, identical or different, independently represent 0 or an integer or decimal number less than 150, q or r is not equal to 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 linear or branched C6-C40-alkyl group, a phenyl group, a polyphenyl group, preferably a linear or branched C10-C30-alkyl group, more preferably a linear or branched C12-C22-alkyl group, or a group comprising 2 with 5 phenyls or a tristy-rylphenyl group or a pentastyrylcumylphenyl group,preferably less than 20 mol%, preferably from 0.05 to 20 mol%, in particular from 0.1 to 10 mol%, of compound (d) relative to the total molar amount of compounds involved.

11. A rheological control composition comprising at least one copolymer P according to any one of claims 1 to 10, optionally acid-treated to a pH below 8, preferably above 6, for example by means of an acid, in particular by for example a carboxylic acid such as acetic acid or lactic acid.

12. Rheological control composition according to claim 11 also comprising at least water or a solvent, in particular a coalescing solvent, for example glycol, butyl glycol, butyldiglycol, monopropylene glycol, ethylene glycol, ethylenediglycol, "Dowanol" products of CAS number 34590-94-8, "Texanol" products of 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.

13. Aqueous formulation comprising: - at least one composition according to any one of claims 11 or 12; 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.

14. Formulation according to claim 13 of coating, in particular an ink formulation, a varnish formulation, an adhesive formulation, a paint formulation, for example decorative paint or industrial paint.

15. Concentrated aqueous pigment paste comprising at least one copolymer P according to any one of claims 1 to 10 and at least one organic or mineral coloured pigment.

16. 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 10 in this composition.

17. Method according to claim 16 wherein the aqueous composition is an aqueous formulation defined according to one of claims 13 or 14.