Thickened ring alkylated urethane copolymers

Abstract

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

Description

[0001] The present invention relates to using a straight chain or branched C 4 -C 24 -alkyl or straight chain or branched C 4 -C 24 The invention also relates to a process for preparing the copolymer and its use in aqueous compositions, in particular in coating compositions.

[0002] Many technical fields require the use of aqueous compositions. These aqueous compositions include in particular aqueous hydraulic binder compositions, aqueous adhesive compositions, aqueous detergent compositions, aqueous cosmetic compositions, aqueous ink compositions, aqueous paper coating compositions, aqueous coating compositions, in particular aqueous varnish compositions or aqueous paint compositions, such as aqueous decorative paint compositions or aqueous industrial paint compositions. In addition to their functional properties, these aqueous compositions must have a texture adapted to their use or their storage. In particular, they must have a suitable viscosity. In addition, it must be possible to use these aqueous compositions under very different conditions. In particular, the viscosity of these aqueous compositions can be varied or reduced.

[0003] If the rheological behavior of these aqueous compositions is not adapted, for example to prevent sedimentation phenomena or phase separation phenomena during their storage, which can also be manifested as changes in viscosity, their functional properties may be altered as a result. Such changes or degradations are particularly harmful or destructive for aqueous hydraulic binder compositions, aqueous adhesive compositions, aqueous detergent compositions, aqueous cosmetic compositions, aqueous ink compositions, aqueous paper coating compositions, aqueous coating compositions, in particular aqueous varnish compositions or aqueous paint compositions.

[0004] Therefore, there is a need for aqueous compositions that do not have such disadvantages or that do not cause such problems.

[0005] In particular, aqueous coating compositions, especially aqueous varnish compositions or aqueous paint compositions, which can have a viscosity adapted to maintain the uniformity and integrity of their functional properties are particularly useful. It should be possible to maintain the viscosity of these aqueous compositions and limit the loss of viscosity over a wide range of shear rates.

[0006] Therefore, many aqueous coating compositions use rheology-modifying polymers. These polymers should be able to impart the desired rheological properties to the aqueous compositions over a wide range of shear rates. These polymers should also improve their shear thinning by imparting sufficient pseudoplastic behavior to the aqueous compositions, ensure their stability and uniformity during their storage, facilitate their transfer to the application tool, and help limit the appearance of droplets once they are applied. The compatibility of the various ingredients in the aqueous coating composition must also be considered. It is particularly important that the thickening copolymer has appropriate compatibility with the pigment and binder used.

[0007] It is likewise important to improve the pigment compatibility of aqueous coating compositions, in particular paint compositions, and in particular with respect to added pigment concentrates for coloring.

[0008] Without good pigment compatibility, the rheology of the composition can be severely degraded. Inadequate pigment compatibility can also result in reduced tinting strength and lead to uneven or washed-out color shades, which can lead to the use of greater amounts of pigment or to aesthetic defects in the final coating.

[0009] Documents WO 2012172249 and WO 2013072592 describe paint formulations thickened with nonionic associative polymers comprising an alkyl group derived from 4-alkyl-cyclohexanol. Document WO 2020084200 describes the preparation of urethane polymers by reactive extrusion.

[0010] Known polymers used as thickeners do not always provide satisfactory solutions to these various problems. Therefore, there is a need for improved rheology-modifying copolymers. The copolymers according to the invention can provide solutions to all or part of the problems of the polymers of the prior art.

[0011] The present invention therefore provides a copolymer P prepared by polymerization of at least one of:

[0012] ● at least one isocyanate compound (a) independently selected from diisocyanate compounds (a1), polyisocyanate compounds (a2) and combinations thereof;

[0013] ● at least one polyhydroxylated compound (b);

[0014] ● At least one compound (c) of formula I:

[0015] RC 6 H 10 -Q m -OH (I)

[0016] in:

[0017] -R independently represents a straight chain C 4 -C 24 -alkyl, branched C 4 -C 24 -alkyl, straight chain C 4 -C 24 -Alkylene, branched C 4 -C 24 -alkylene groups and combinations thereof;

[0018] -m independently represents 0 or a number from 1 to 100;

[0019] -Q represents a group selected from oxyethylene, oxypropylene, oxybutylene and combinations thereof.

[0020] Preferably, for the copolymer P according to the invention, the isocyanate compound (a) is a diisocyanate compound (a1) selected from:

[0021] - Symmetrical aromatic diisocyanate compounds, which are preferably:

[0022] ●2,2'-diphenylmethylene diisocyanate (2,2'-MDI) and 4,4'-diphenylmethylene diisocyanate (4,4'-MDI);

[0023] ●4,4'-dibenzyl diisocyanate (4,4'-DBDI);

[0024] ●2,6-Toluene diisocyanate (2,6-TDI);

[0025] ●m-Xylylene diisocyanate (m-XDI);

[0026] - a symmetrical alicyclic diisocyanate compound, which is preferably methylenebis(4-cyclohexyl isocyanate) (H 12 MDI);

[0027] - symmetrical aliphatic diisocyanate compounds, which are preferably hexamethylene diisocyanate (HDI) and pentamethylene diisocyanate (PDI);

[0028] - an asymmetric aromatic diisocyanate compound, which is preferably:

[0029] ●2,4'-diphenylmethylene diisocyanate (2,4'-MDI);

[0030] ●2,4'-dibenzyl diisocyanate (2,4'-DBDI);

[0031] ●2,4-Toluene diisocyanate (2,4-TDI);

[0032] - an asymmetric alicyclic diisocyanate compound, which is preferably isophorone diisocyanate (IPDI).

[0033] More preferably, according to the present invention, compound (a1) is selected from IPDI, HDI, H 12 MDI and its combinations.

[0034] Also preferably, for the copolymer P according to the invention, the isocyanate compound (a) may be a polyisocyanate compound (a2) strictly comprising more than 2 isocyanate groups or more than 2.2 isocyanate groups or even more than 2.5 isocyanate groups. More preferably, the polyisocyanate compound (a2) comprises more than 2.6 isocyanate groups or more than 2.7 isocyanate groups or more than 3 isocyanate groups. Still more preferably, the polyisocyanate compound (a2) comprises 2.2 to 6 isocyanate groups, 2.2 to 4 isocyanate groups, 2.2 to 3.5 isocyanate groups, 2.5 to 6 isocyanate groups, 2.2 to 5 isocyanate groups, 2.5 to 4 isocyanate groups, 2.5 to 3.5 isocyanate groups, in particular 2.6 to 3.3 isocyanate groups.

[0035] Also preferably, the polyisocyanate compound (a2) is selected from:

[0036] - triphenylmethane-4,4',4"-triisocyanate or 1,1',1"-methylenetris(4-isocyanatobenzene);

[0037] - an isocyanurate compound, in particular an isocyanurate compound selected from the group consisting of:

[0038] ■ Symmetrical aromatic diisocyanate compounds, preferably:

[0039] ●2,2'-diphenylmethylene diisocyanate (2,2'-MDI) and 4,4'-diphenylmethylene diisocyanate (4,4'-MDI);

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

[0041] ●2,6-Toluene diisocyanate (2,6-TDI);

[0042] ●m-Xylylene diisocyanate (m-XDI);

[0043] ■ Symmetrical alicyclic diisocyanate compounds, preferably methylenebis(4-cyclohexyl isocyanate) (H 12 MDI);

[0044] ■ Symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI) and pentamethylene diisocyanate (PDI);

[0045] ■Asymmetric aromatic diisocyanate compounds, preferably:

[0046] ●2,4'-diphenylmethylene diisocyanate (2,4'-MDI);

[0047] ●2,4'-dibenzyl diisocyanate (2,4'-DBDI);

[0048] ●2,4-Toluene diisocyanate (2,4-TDI);

[0049] - a biuret trimer compound, in particular a biuret trimer compound selected from the group consisting of:

[0050] ■ Symmetrical aromatic diisocyanate compounds, preferably:

[0051] ●2,2'-diphenylmethylene diisocyanate (2,2'-MDI) and 4,4'-diphenylmethylene diisocyanate (4,4'-MDI);

[0052] ●4,4'-dibenzyl diisocyanate (4,4'-DBDI);

[0053] ●2,6-Toluene diisocyanate (2,6-TDI);

[0054] ●m-Xylylene diisocyanate (m-XDI);

[0055] ■ Symmetrical alicyclic diisocyanate compounds, preferably methylenebis(4-cyclohexyl isocyanate) (H 12 MDI);

[0056] ■ Symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI) and pentamethylene diisocyanate (PDI);

[0057] ■Asymmetric aromatic diisocyanate compounds, preferably:

[0058] ●2,4'-diphenylmethylene diisocyanate (2,4'-MDI);

[0059] ●2,4'-dibenzyl diisocyanate (2,4'-DBDI);

[0060] ●2,4-Toluene diisocyanate (2,4-TDI);

[0061] ■ An asymmetric alicyclic diisocyanate compound, preferably isophorone diisocyanate (IPDI).

[0062] More preferably, compound (a2) is selected from triphenylmethane-4,4',4"-triisocyanate, 1,1',1"-methylenetris(4-isocyanatobenzene), HDI isocyanurate, IPDI isocyanurate, PDI isocyanurate, HDI biuret trimer and IPDI biuret trimer, PDI biuret trimer.

[0063] According to the present invention, the polyisocyanate compound (a2) is different from the diisocyanate compound (a1).

[0064] Preferably, for the copolymer P according to the invention, the polyhydroxylated compound (b) is a compound (b1) of formula II:

[0065] HO-L n -OH (II)

[0066] in:

[0067] -L independently represents an oxyalkylene residue;

[0068] -n independently represents a number from 30 to 1000.

[0069] Preferably, for the copolymer P according to the invention, the polyhydroxylated compound (b) is a compound (b1) of formula II, wherein:

[0070] -L independently represents an oxyalkylene residue; or

[0071] -n independently represents a number from 50 to 400, preferably a number from 100 to 300.

[0072] More preferably, for the copolymers P according to the invention, the polyhydroxylated compound (b) is a compound (b1) of formula II, wherein L independently represents an oxyalkylene residue and p independently represents a number from 50 to 400, preferably from 100 to 300.

[0073] According to the present invention, the compound (b1) of formula II can be combined with a non-alkoxy compound (b2) comprising at least three hydroxyl groups. Preferably, according to the present invention, compound (b2) comprises three hydroxyl groups. More preferably, it is selected from glycerol, pentaerythritol and a combination thereof. According to the present invention, the polyhydroxylated compound (b) can also be a polyethoxylated pentaerythritol or a polyalkoxylated compound (b3) comprising at least three hydroxyl groups. Preferably, according to the present invention, compound (b3) is different from compound (b2) and comprises three hydroxyl groups. More preferably, it is a polyethoxylated glycerol.

[0074] Advantageously, according to the present invention, the copolymer P can be prepared using one or a combination of more than one of compound (b1), compound (b2) and compound (b3).

[0075] Preferably, according to the present invention, compound (b), compound (b1) or compound (b3) independently has a molar mass (Mw) measured by SEC of 1500 g / mol to 40000 g / mol, preferably 2000 g / mol to 20000 g / mol, more preferably 2000 g / mol to 15000 g / mol or 2000 g / mol to 12000 g / mol.

[0076] According to the present invention, the molar mass of compound (b), compound (b1) or compound (b3) is measured by size exclusion chromatography (SEC), also known as "gel permeation chromatography" (GPC). This technique uses a "Waters" liquid chromatograph equipped with a detector. The detector is a "Waters" 2414 refractive index detector. The liquid chromatograph is equipped with two size exclusion columns for separating the polymers with different molecular weights or compounds with different molecular weights studied. The liquid elution phase is an organic phase containing THF (HPLC grade, not stabilized). In the first step, about 25 mg of the compound is dissolved in 5 mL of THF, to which 0.1 mol% of water is added as an internal flow marker. Subsequently, the solution is filtered through a 0.2 μm filter. Then 50 μL is injected into the chromatograph (eluent: THF, HPLC grade, not stabilized). The liquid chromatograph has an isocratic pump ("Waters" 515) with a flow rate set to 0.3 ml / min. The chromatograph also includes a column oven, which includes a column system in series: an "Agilent" PLgel MiniMIX-A column with a column length of 250 mm and a diameter of 4.6 mm, followed by an "Agilent" PLgel MiniMIX-B column with a column length of 250 mm and a diameter of 4.6 mm. The detection system includes a "Waters" 2414RI refractive index detector. The chromatographic column is maintained at a temperature of 35°C and the refractometer is heated to 35°C. The chromatographic instrument is calibrated using a polymethyl methacrylate standard ("EasiVial" PMMA) certified by the supplier "Agilent".

[0077] Preferably, according to the present invention, compound (c) is a compound of formula I, wherein R independently represents a linear C 4 -C 24 -alkyl or linear C 4 -C 24 -alkylene group, preferably a straight chain C 6 -C 20 -alkyl or linear C 6 -C 20-alkylene, more preferably a straight chain C 12 -C 18 -alkyl or linear C 12 -C 18 -alkylene, more preferably a straight chain C 15 -alkyl.

[0078] According to the present invention, the alkylene group may contain 1 to 6 unsaturated bonds, preferably 1, 2 or 3 unsaturated bonds. Preferred alkylene groups contain a single unsaturated bond, preferably a single terminal unsaturated bond. In fact, the unsaturated bond in the alkylene group may be a terminal unsaturated bond or may also be present in the alkylene chain.

[0079] Preferably, according to the invention, compound (c) is a compound of formula I, wherein m independently represents 0 or a number from 2 to 50, or a number from 2 to 20, or even a number from 2 to 10.

[0080] Preferably, according to the present invention, compound (c) is a compound of formula I, wherein Q represents oxyethylene or a combination of oxyethylene and oxypropylene, preferably, the molar ratio (oxyethylene / oxypropylene) is 95 / 5 to 50 / 50, preferably 80 / 50 to 70 / 30 or 65 / 35 to 55 / 45.

[0081] More preferably, according to the present invention, compound (c) is a compound of formula I, wherein:

[0082] -R independently represents a linear C 4 -C 24 -alkyl or linear C 4 -C 24 -alkylene group, preferably a straight chain C 6 -C 20 -alkyl or linear C 6 -C 20 -alkylene, more preferably a straight chain C 12 -C 18 -alkyl, straight chain C 12 -C 18 -alkylene, more preferably a straight chain C 15 -alkyl,

[0083] - m independently represents 0 or a number from 2 to 50 or from 2 to 20 or from 2 to 10; and

[0084] -Q represents oxyethylene or a combination of oxyethylene and oxypropylene, preferably, the molar ratio (oxyethylene / oxypropylene) is 95 / 5 to 50 / 50, preferably 80 / 50 to 70 / 30 or 65 / 35 to 55 / 45.

[0085] More preferably, according to the present invention, compound (c) is a compound of formula I, wherein:

[0086] -R independently represents a linear C 4 -C 24 -alkyl group, preferably a straight chain C 6 -C 20 -alkyl, more preferably a straight chain C 12 -C 18 -alkyl, more preferably a straight chain C 15 -alkyl,

[0087] - m independently represents 0 or a number from 2 to 50 or from 2 to 20 or from 2 to 10; and

[0088] -Q represents oxyethylene or a combination of oxyethylene and oxypropylene, preferably, the molar ratio (oxyethylene / oxypropylene) is 95 / 5 to 50 / 50, preferably 80 / 50 to 70 / 30 or 65 / 35 to 55 / 45.

[0089] Preferably, according to the present invention, compound (c) is a compound of formula I, wherein R independently represents a linear alkyl group.

[0090] The compound (c) according to the present invention is a compound of formula I, which comprises a C containing 6 carbon atoms and which is cyclic 6 H 10 Group.

[0091] When preparing copolymer P according to the present invention, the amount of compound (a), compound (b) and compound (c) can vary. Preferably, for copolymer P, relative to the total molar amount of monomer (a), monomer (b) and monomer (c), the polymerization reaction uses:

[0092] 10 mol% to 79.9 mol%, or 10 mol% to 74.5 mol%, preferably 10 mol% to 68 mol%, or 10 mol% to 60 mol%, of monomer (a), or

[0093] 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

[0094] - 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).

[0095] More preferably, according to the present invention, the polymerization reaction may use, relative to the total molar amount of monomer (a), monomer (b) and monomer (c):

[0096] - 10 mol% to 79.9 mol%, or 10 mol% to 74.5 mol% of monomer (a),

[0097] - 20 mol% to 89.9 mol%, or 25 mol% to 89.5 mol% of monomer (b), and

[0098] - 0.1 mol% to 70 mol%, or 0.5 mol% to 65 mol%, of monomer (c).

[0099] Even more preferably, according to the present invention, the polymerization reaction may use, relative to the total molar amount of monomer (a), monomer (b) and monomer (c):

[0100] - 10 mol% to 68 mol%, or 10 mol% to 60 mol% of monomer (a),

[0101] - 30 mol% to 88 mol%, or 35 mol% to 85 mol% of monomer (b), and

[0102] - 2 mol% to 60 mol%, or 5 mol% to 55 mol% of monomer (c).

[0103] According to the present invention, the polymerization reaction can use only compound (a), compound (b) and compound (c), or use one or more than one other additional compound. Therefore, the polymerization reaction can also use at least one hydrophobic compound (d) different from compound (c), preferably a compound selected from formula (III):

[0104] R 1 -(EO) q -(PO) r -OH(Ⅲ)

[0105] in:

[0106] -q and r, identical or different, independently represent 0 or an integer or a decimal less than 150; in particular, q or r is different from 0,

[0107] -EO independently represents CH 2 CH 2 O group,

[0108] -PO independently represents a 3 )CH 2 O and CH 2 CH(CH 3 )O group,

[0109] -R 1 Independently represent straight or branched C 4 -C 40 -alkyl, preferably a straight chain or branched C 6 -C 30 -alkyl, more preferably a straight chain or branched C6 -C 22 -alkyl.

[0110] Preferably, the polymerization reaction can use less than 60 mol %, preferably 0.05 mol % to 60 mol %, especially 0.1 mol % to 60 mol %, more preferably less than 50 mol %, preferably 0.05 mol % to 50 mol %, especially 0.1 mol % to 50 mol %, relative to the total molar amount of the compounds used.

[0111] The copolymers P according to the invention can be used in many technical fields, in particular as rheology control agents. They can be incorporated into different compositions. Therefore, the present 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 to a pH above 6. The treatment can be carried out with an acid, in particular a carboxylic acid, such as acetic acid or lactic acid.

[0112] The rheology control composition according to the invention may also contain at least one solvent, in particular water or a coalescing solvent, such as glycols, butyl glycol, diethylene glycol butyl ether, monopropylene glycol, ethylene glycol, diethylene glycol, the "Dowanol" product with CAS No. 34590-94-8, the "Texanol" product with CAS No. 25265-77-4; or a combination of at least one additive selected from amphiphilic compounds, in particular surfactant compounds, preferably hydroxylated surfactant compounds, such as alkyl-polyalkylene glycols, in particular alkyl-polyethylene glycol and alkyl-polypropylene glycol; polysaccharide derivatives, such as cyclodextrins, cyclodextrin derivatives, polyethers, alkyl-glycosides; hydrotropic compounds, defoamers, antimicrobial agents and combinations thereof.

[0113] The rheology control composition according to the invention is particularly suitable for facilitating the use of pigments, in particular organic or inorganic pigments, in aqueous media. It can be incorporated into specific pigment preparations. Therefore, the present invention provides an aqueous preparation comprising:

[0114] - at least one rheology controlling composition according to the invention; optionally

[0115] at least one organic or inorganic pigment or organic, organometallic or inorganic particle, for example calcium carbonate, talc, kaolin, mica, silicates, silicon dioxide, metal oxides, in particular titanium dioxide, iron oxides; and optionally

[0116] - at least one agent selected from particle spacing agents, dispersants, steric stabilizers, electrostatic stabilizers, opacifiers, colorants, solvents, coalescing agents, defoamers, preservatives, antimicrobial agents, extenders, thickeners, film-forming copolymers and mixtures thereof.

[0117] Preferably, the preparation according to the invention is a coating preparation, in particular an ink preparation, a varnish preparation, an adhesive preparation, a paint preparation, for example a decorative paint preparation or an industrial paint preparation.

[0118] The copolymers P according to the invention can also be used in the printing sector, in particular textile printing. The invention therefore provides concentrated aqueous pigment slurries comprising at least one copolymer P according to the invention and at least one colored organic pigment or colored inorganic pigment.

[0119] The invention also provides a method for controlling the viscosity of an aqueous composition, which comprises adding to the composition at least one copolymer P according to the invention. The viscosity control method according to the invention is used for aqueous compositions of aqueous preparations according to the invention.

[0120] Advantageous, particular or preferred features of the copolymers P according to the invention define likewise advantageous, particular or preferred rheology-controlling compositions, aqueous preparations, pigment slurries and viscosity-controlling methods according to the invention.

[0121] The following examples illustrate various aspects of the invention. Example:

[0122] Example 1: Preparation of copolymer P according to the invention:

[0123] The copolymer P1 according to the invention:

[0124] In a 2L glass reactor with double jacket heating equipped with a mechanical stirring rod, a vacuum pump and a nitrogen inlet and using oil circulation, compound (b) (polyethylene glycol-molecular weight 10000 g / mol) (154.5 g) was introduced and heated to 95° C. under vacuum. Subsequently, 0.33 g of DBU catalyst (1,8-diazabicyclo[5.4.0]undec-7-ene) was added to the medium under stirring and inert atmosphere, followed by the addition of compound (c1) (hydrogenated cardanol, wherein R represents a linear C 15 -alkyl and m represents 0 (formula I) (7.7 g) and dodecan-1-ol (4.6 g). Subsequently, a diisocyanate compound (a1) (isophorone diisocyanate, IPDI) (11 g) was introduced using a syringe and stirred at 150 rpm. The reaction was continued at 100° C. for 1 hour.

[0125] Then, the isocyanate content is checked by backtesting to ensure that it is zero. Collect 1 gram of reaction medium, add excess dibutylamine (for example, 1 mole) thereto, it can react with any isocyanate groups that may be present in the medium. Then, analyze any unreacted dibutylamine with hydrochloric acid (for example, 1 equivalent concentration). Then, the number of isocyanate groups present in the reaction medium can be inferred. If this value is not zero, the reaction is continued for 15 minutes until the reaction is complete. Use ethoxylated alcohol surfactant compounds ("Emulan" HE 51 "Basf") (48.3g) and ("Simulsol" Ox1008 "Seppic") (48.3g), 1000ppm of antimicrobial agent ("Biopol" SMV "Chemipol"), 1000ppm of defoamer ("Tego" 1488 "Evonik") and water (725g) to prepare copolymer P1. This gave an aqueous rheology control composition composed of 17.5% by mass of copolymer P1 according to the invention, 9.5% by mass of a surfactant compound and 73% by mass of water.

[0126] The copolymer P2 according to the invention:

[0127] In a 2L glass reactor equipped with a mechanical stirring rod, a vacuum pump and a nitrogen inlet and heated with a double jacket using oil circulation, compound (b) (polyethylene glycol-molecular weight 10000 g / mol) (151.5 g) was introduced and heated to 95 ° C under vacuum. Subsequently, under stirring and inert atmosphere, 0.33 g of DBU catalyst was added to the medium, followed by addition of compound (c1) (hydrogenated cardanol) (7.7 g), dodecanol (3.4 g) and octan-1-ol (0.6 g) within 15 minutes. Subsequently, a syringe was used and diisocyanate compound (a1) (isophorone diisocyanate, IPDI) (10.8 g) was introduced under stirring at 150 rpm. The reaction continued for 1 hour at 100 ° C.

[0128] Subsequently, the isocyanate content was checked by backtesting to ensure that it was zero. Copolymer P2 was formulated using ethoxylated alcohol surfactant compounds ("Emulan" HE51 "Basf") (48.3 g) and ("Simulsol" Ox1008 "Seppic") (48.3 g), 1000 ppm of an antimicrobial agent ("Biopol" SMV "Chemipol"), 1000 ppm of a defoamer ("Tego" 1488 "Evonik") and water (725 g). This gave an aqueous rheology control composition consisting of 17.5% by mass of the copolymer P2 according to the invention, 9.5% by mass of surfactant compounds and 73% by mass of water.

[0129] Example 2: Preparation and characterization of aqueous paint formulations according to the invention:

[0130] A matt paint formulation F1 according to the invention was prepared by mixing the various ingredients under stirring. The compounds used and the amounts (g) are listed in Table 1.

[0131] Composition of matt paint preparations Amount (g) "Ecodis" P50 ("Coatex" dispersant) 0.4 "Tego" 825 ("Tego" defoamer) 0.1 MBS "Acticide" ("Thor" fungicide) 0.2 <![CDATA["Tiona”568("Tronox”TiO 2 )]]> 8.1 <![CDATA["Omyacoat”850 OG("Omya”CaCO 3 )]]> 13.1 <![CDATA["Durcal”2 AV("Omya”CaCO 3 )]]> 30.3 ″Mowilith”LDM1871 (“Celanese” adhesive) 15.1 NaOH (20% in water) 0.1 Aqueous composition of copolymer P1 2.2 water 30.4 total 100.00

[0132] Table 1

[0133] Subsequently, the paint formulation F1 was pigmented by adding 5% by weight of a black pigment (“Colanyl” N500 black “Clariant”) to give the pigmented formulation F1 according to the invention.

[0134] Subsequently, for the coloured formulation F1, the following data were measured at 25°C:

[0135] ●Brookfield viscosity at 10 rpm (μB10, mPa.s);

[0136] ●Brookfield viscosity at 100rpm (μB100, mPa.s);

[0137] Cone-and-plate viscosity or ICI viscosity measured under high shear gradient (μI, mPa.s);

[0138] • Stormer viscosity (μS, Krebs units or KU) measured under moderate shear gradient using a reference modulus.

[0139] The results are shown in Table 2. The results were measured immediately after the addition of the black pigment (T=0) and 24 hours after the addition (T=24 hours).

[0140] The pigment compatibility of formulation F1 was evaluated on dried paint coatings.

[0141] The rub-out test is known per se and involves rubbing a 150 micron thick wet colored paint layer on a comparison chart with a finger. This may expose a small portion of the surface of the newly applied colored paint layer to the shearing effect generated by the circular motion of the finger. The shearing effect may change the stability and distribution of the colored pigments in the matrix consisting of the colored paint layer, thereby changing the color intensity of the sheared area.

[0142] When the pigmented paint layer has dried, the color difference between the initial sheared area and the unsheared area of ​​the pigmented paint layer is measured using a Spectro-Guide Sphere Gloss spectrophotometer sold by "Byk".

[0143] The color difference is quantified by a ΔE value calculated from the known measured parameters corresponding to the L*a*b* color space. Low ΔE values ​​indicate a reduced color difference between sheared and unclipped areas, thus improving pigment compatibility.

[0144] The unsheared area of ​​the colored paint was also measured according to one of the parameters of the L*a*b* color space. The parameter L* quantifies the color intensity. Low L* values ​​indicate reduced lightness and therefore higher black intensity, corresponding to improved pigment compatibility of the paint formulations evaluated in which the copolymers according to the present invention are used. The results are shown in Table 2.

[0145]

[0146] Table 2

[0147] For the pigmented preparation F1 according to the invention, the copolymers according to the invention make it possible to control the viscosity of the various ingredients both after preparation and over time. The copolymers according to the invention impart good pigment compatibility to the paint preparation.

Claims

1. A copolymer P prepared by polymerization of at least one of the following: ● at least one isocyanate compound (a) independently selected from diisocyanate compounds (a1), polyisocyanate compounds (a2) and combinations thereof; ● at least one polyhydroxylated compound (b); ● At least one compound (c) of formula I: R-C6H 10 -Q m -OH (I) in: -R independently represents a straight chain C4-C 24 -alkyl, branched C4-C 24 -alkyl, straight chain C4-C 24 -Alkylene, branched C4-C 24 -alkylene groups and combinations thereof; -m independently represents 0 or a number from 1 to 100; -Q represents a group selected from oxyethylene, oxypropylene, oxybutylene and combinations thereof.

2. The copolymer P according to claim 1, wherein the isocyanate compound (a) is: ● A diisocyanate compound (a1) 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); - a symmetrical alicyclic diisocyanate compound, preferably methylenebis(4-cyclohexyl isocyanate) (H 12 MDI); - Symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI) and pentamethylene diisocyanate (PDI); - an asymmetric aromatic diisocyanate compound, preferably: ●2,4'-diphenylmethylene diisocyanate (2,4'-MDI); ●2,4'-dibenzyl diisocyanate (2,4'-DBDI); ●2,4-Toluene diisocyanate (2,4-TDI); - an asymmetric alicyclic diisocyanate compound, preferably isophorone diisocyanate (IPDI), More preferably, the compound (a1) is selected from IPDI, HDI, H 12 MDI and its combination; or a polyisocyanate compound (a2) which strictly comprises more than 2 isocyanate groups or more than 2.2 isocyanate groups or even more than 2.5 isocyanate groups; preferably, the polyisocyanate compound (a2) comprises more than 2.6 isocyanate groups or more than 2.7 isocyanate groups or more than 3 isocyanate groups; more preferably, the polyisocyanate compound (a2) comprises 2.2 to 6 isocyanate groups, 2.2 to 4 isocyanate groups, 2.2 to 3.5 isocyanate groups, 2.5 to 6 isocyanate groups, 2.2 to 5 isocyanate groups, 2.5 to 4 isocyanate groups, 2.5 to 3.5 isocyanate groups, in particular 2.6 to 3.3 isocyanate groups; or A polyisocyanate compound (a2) selected from: - triphenylmethane-4,4',4"-triisocyanate or 1,1',1"-methylenetris(4-isocyanatobenzene); - an isocyanurate compound, in particular an isocyanurate compound selected from the group consisting of: ■ 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 methylenebis(4-cyclohexyl isocyanate) (H 12 MDI); ■ Symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI) and pentamethylene diisocyanate (PDI); ■Asymmetric 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); - a biuret trimer compound, in particular a biuret trimer compound selected from the group consisting of: ■ 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 methylenebis(4-cyclohexyl isocyanate) (H 12 MDI); ■ Symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI) and pentamethylene diisocyanate (PDI); ■Asymmetric 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); ■ an asymmetric alicyclic diisocyanate compound, preferably isophorone diisocyanate (IPDI), Preferably, the compound (a2) is selected from triphenylmethane-4,4',4"-triisocyanate, 1,1',1"-methylenetris(4-isocyanatebenzene), HDI isocyanurate, IPDI isocyanurate, PDI isocyanurate, HDI biuret trimer, IPDI biuret trimer, PDI biuret trimer.

3. The copolymer P according to any one of claims 1 or 2, wherein the polyhydroxylated compound (b) is selected from: ●Compound (b1) of formula II: HO-L n -OH (II) in: -L independently represents an oxyalkylene residue; -n independently represents a number from 30 to 1000; A compound (b1) of formula II in combination with a non-alkoxylated compound (b2) comprising at least three hydroxyl groups; A polyalkoxylated compound (b3) comprising at least three hydroxyl groups; ●Their combination.

4. The copolymer P according to any one of claims 1 to 3, wherein the compound (b) is selected from: ● A compound (b1) of formula II, wherein: -L independently represents an oxyalkylene residue; or - n independently represents a number from 50 to 400, preferably a number from 100 to 300; or - L independently represents an oxyalkylene residue, and p independently represents a number from 50 to 400, preferably a number from 100 to 300; A compound (b2) comprising three hydroxyl groups, which is preferably selected from glycerol, pentaerythritol and combinations thereof; • A compound (b3) which is different from compound (b2) and contains three hydroxyl groups, preferably compound (b3) is polyethoxylated glycerol or polyethoxylated pentaerythritol.

5. The copolymer P according to any one of claims 1 to 4, wherein the compound (b), compound (b1) or compound (b3) independently has a molar mass (Mw) measured by SEC of 1500 g / mol to 40000 g / mol, preferably 2000 g / mol to 20000 g / mol, more preferably 2000 g / mol to 15000 g / mol or 2000 g / mol to 12000 g / mol.

6. The copolymer P according to any one of claims 1 to 5, wherein the compound (c) is a compound of formula I, wherein: -R independently represents a linear C4-C 24 -alkyl or straight chain C4-C 24 -alkylene group, preferably a straight chain C6-C 20 -alkyl or straight chain C6-C 20 -alkylene, more preferably a straight chain C 12 -C 18 -alkyl or linear C 12 -C 18 -alkylene, more preferably a straight chain C 15 -alkyl; 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 oxyethylene or a combination of oxyethylene and oxypropylene, preferably, the molar ratio (oxyethylene / oxypropylene) is 95 / 5 to 50 / 50, preferably 80 / 50 to 70 / 30 or 65 / 35 to 55 / 45.

7. The copolymer P according to any one of claims 1 to 6, wherein the polymerization reaction uses, relative to the total molar amount of monomer (a), monomer (b) and monomer (c): 10 mol% to 79.9 mol%, or 10 mol% to 74.5 mol%, preferably 10 mol% to 68 mol%, or 10 mol% to 60 mol%, of monomer (a), or 20 mol% to 89.9 mol%, or 25 mol% to 89.5 mol%, preferably 30 mol% to 88 mol%, or 35 mol% to 85 mol%, of monomer (b), or - 0.1 mol% to 70 mol%, or 0.5 mol% to 65 mol%, preferably 2 mol% to 60 mol%, or 5 mol% to 55 mol%, of monomer (c).

8. The copolymer P according to any one of claims 1 to 7, wherein the polymerization reaction also uses at least one hydrophobic compound (d) different from compound (c), which is preferably selected from compounds of formula (III): R 1 -(EO) q -(PO) r -OH(III) in: -q and r, identical or different, independently represent 0 or an integer or a decimal less than 150; in particular, q or r is different from 0, -EO independently represents a CH2CH2O group, -PO independently represents a group selected from CH(CH3)CH2O and CH2CH(CH3)O, -R 1 Independently represent a straight or branched C4-C 40 -alkyl, preferably a linear or branched C6-C 30 -alkyl, more preferably a linear or branched C6-C 22 -alkyl, relative to the total molar amount of the compounds used, compound (d) is preferably less than 60 mol%, preferably 0.05 mol% to 60 mol%, especially 0.1 mol% to 60 mol%, more preferably less than 50 mol%, preferably 0.05 mol% to 50 mol%, especially 0.1 mol% to 50 mol%.

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

10. The rheology control composition according to claim 9, further comprising at least one solvent, in particular water or a coalescing solvent, such as glycols, butyl glycol, diethylene glycol butyl ether, monopropylene glycol, ethylene glycol, diethylene glycol, the "Dowanol" product with CAS No. 34590-94-8, the "Texanol" product with CAS No. 25265-77-4; or in combination with at least one additive selected from amphiphilic compounds, in particular surfactant compounds, preferably hydroxylated surfactant compounds, such as alkyl-polyalkylene glycols, in particular alkyl-polyethylene glycol and alkyl-polypropylene glycol; polysaccharide derivatives, such as cyclodextrins, cyclodextrin derivatives, polyethers, alkyl-glycosides; hydrotropic compounds, defoamers, antimicrobial agents and combinations thereof.

11. An aqueous preparation comprising: - at least one composition according to any one of claims 9 or 10; optionally at least one organic or inorganic pigment or organic, organometallic or inorganic particle, for example calcium carbonate, talc, kaolin, mica, silicates, silicon dioxide, metal oxides, in particular titanium dioxide, iron oxides; and optionally - at least one agent selected from particle spacing agents, dispersants, steric stabilizers, electrostatic stabilizers, opacifiers, colorants, solvents, coalescing agents, defoamers, preservatives, antimicrobial agents, extenders, thickeners, film-forming copolymers and mixtures thereof.

12. The preparation according to claim 11, which is a coating preparation, in particular an ink preparation, a varnish preparation, an adhesive preparation, a paint preparation, for example a decorative paint preparation or an industrial paint preparation.

13. A concentrated aqueous pigment slurry comprising at least one copolymer P according to any one of claims 1 to 8 and at least one coloured organic pigment or coloured inorganic pigment.

14. A method for controlling the viscosity of an aqueous composition, comprising adding to the composition at least one copolymer P according to any one of claims 1 to 8.

15. The method according to claim 14, wherein the aqueous composition is an aqueous formulation as defined in any one of claims 11 or 12.

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