NON-STICK MATERIAL

Abstract

The present invention relates to a material with non-stick and / or anti-fouling properties, its preparation process and its use in various applications for which a non-stick and / or anti-fouling effect is desired.

Description

Title of the invention: ANTI-STICK MATERIAL FIELD OF INVENTION

[0001] The present invention relates to a material with anti-stick and / or anti-fouling properties, its preparation process and its use in various applications for which an anti-stick and / or anti-fouling effect is desired. STATE OF THE ART

[0002] In many applications, the use of materials with non-stick and / or anti-fouling properties is useful for obtaining surfaces that are easy to clean and durable. Most of the time, such properties are obtained by applying a particular coating composition to the surface of the material in question. For example, application EP3023467 describes the preparation of coating compositions comprising polysiloxanes capable of imparting a non-stick and / or anti-fouling effect to the surfaces on which such compositions are applied. However, the coatings are likely to deteriorate over time, so they must be reapplied to maintain the desired properties. Furthermore, it is necessary to ensure the compatibility between the coating composition and that of the surface to be coated.US patents 6,127,507 and 9,713,049 propose using copolymers as additives within a matrix of the same chemical nature. The copolymer incorporates perfluorinated ends to give the material anti-stick properties. However, the incompatibility between these perfluorinated copolymers and the polyurethane matrix makes the use of these materials complex to implement.

[0003] A need therefore remains for a material with non-stick and / or anti-fouling properties, which is versatile, and for which the non-stick and / or anti-fouling effect is maintained throughout the entire period of use.

[0004] In particular, such a material may be useful for the preparation of medical devices for which the anti-stick and / or anti-fouling properties make it possible to repel undesirable substances present in bodily fluids.

[0005] The present invention aims to provide a material with anti-stick and / or anti-fouling properties, useful in various fields, whose manufacture is industrially adapted and which is durable over time and for the intended application. Description of the invention

[0006] A first object of the present invention relates to a material comprising a polymer matrix in which is dispersed an amphiphilic block copolymer comprising:

[0007] - a hydrophobic block comprising one or more repeating patterns selected from hydrophobic C1-C10 alkyl or aryl methacrylates and their combinations, and

[0008] - a hydrophilic block comprising one or more selected repeating motifs among the poly(ethylene oxide) methacrylates (MAPEG), 2-hydroxy-3-phenoxypropylacrylate (HPhOPA), 4-tert-butylcyclohexyl acrylate (tBCHA), N-hydroxyethylacrylamide (HEAA), N,N-diethylacrylamide (DEAA) and their combinations.

[0009] The present invention also relates to the use of an amphiphilic block copolymer comprising:

[0010] - a hydrophobic block comprising one or more repeating patterns selected from hydrophobic C1-C10 alkyl or aryl methacrylates and their combinations, and

[0011] - a hydrophilic block comprising one or more selected repeating motifs

[0012] among poly(ethylene oxide) methacrylates (MAPEG), 2-hydroxy-3-phenoxypropylacrylate (HPhOPA), 4-tert-butylcyclohexyl acrylate (tBCHA), N-hydroxyethylacrylamide (HEAA), N,N-diethylacrylamide (DEAA) and their combinations

[0013] for the preparation of a material with anti-stick and / or anti-fouling properties.

[0014] The present invention relates to an article with anti-stick and / or anti-fouling properties such as medical devices, packaging, in particular food packaging, containers, furniture, utensils, for example kitchen utensils, filtration membranes, pipes, devices for transporting liquids or biological media (blood bags, nutritional media etc.), textiles, such as for example anti-fouling mats, shoes, clothing, building components, such as for example a door handle, floor coverings, sports facilities, personal protective equipment, comprising a material according to the present invention.

[0015] Finally, the present invention relates to the use of the material as defined above for the preparation of an article with anti-stick and / or anti-fouling properties. DESCRIPTION OF THE FIGURES

[0016] Figure 1 represents a block diagram of the process for preparing a material according to the invention. DETAILED DESCRIPTION OF THE INVENTION

[0017] In the context of the present invention, and unless otherwise indicated, the term “comprising” also includes the meaning of “consisting of”.

[0018] The term "copolymer" refers to a polymer containing several (at least two) different repeating units. A "repeating unit" consists of a A repeating unit is a group of atoms repeated multiple times within a polymer to form the polymer chain. The repeating unit is the group of atoms introduced into the polymer chain by the polymerization of a given monomer. A copolymer can be a random copolymer, an alternating copolymer, a block copolymer, or a gradient copolymer. In the context of this invention, it is a block copolymer.

[0019] The term "block copolymer" refers to a copolymer containing, in particular consisting of, a linear sequence of several different blocks, each block being made up of a homopolymer chain, that is to say, made up of a single repeating unit, two adjacent blocks therefore being made up of different repeating units. A block copolymer constitutes a single macromolecule, such that each block is covalently linked to the next block by a covalent bond.

[0020] The term "statistical copolymer" refers to a copolymer comprising at least two different repeating motifs, in which these different repeating motifs are inserted randomly into the block.

[0021] In the context of the invention, a block of the copolymer can itself be a statistical copolymer.

[0022] In the context of the present invention, the expression "non-stick material" or "material having non-stick properties" indicates that said material has characteristics enabling it to prevent the adhesion of a substance to its surface.

[0023] In the context of the present invention, the expression "antifouling material" or "material having antifouling properties" indicates that said material is capable of resisting the accumulation of dirt, and in particular of repelling it. Antifouling materials are, in fact, easy to clean.

[0024] A first object of the present invention relates to a material comprising a polymer matrix in which is dispersed an amphiphilic block copolymer comprising:

[0025] - a hydrophobic block comprising one or more repeating patterns selected from hydrophobic C1-C10 alkyl or aryl methacrylates and their combinations, and

[0026] - a hydrophilic block comprising one or more selected repeating motifs among the poly(ethylene oxide) methacrylates (MAPEG), 2-hydroxy-3-phenoxypropylacrylate (HPhOPA), 4-tert-butylcyclohexyl acrylate (tBCHA), N-hydroxyethylacrylamide (HEAA), N,N-diethylacrylamide (DEAA) and their combinations.

[0027] In the context of the present invention, the term "hydrophilic block" refers to a block having favorable interactions with water, resulting in solubility and / or swelling capacity. In the context of the present invention, the term "hydrophobic block" refers to a block not having favorable interactions with water. In the context of the present invention, the term "amphiphile" refers to a compound (e.g., a block copolymer) having a hydrophilic part and a hydrophobic part. HYDROPHOBIC BLOCK

[0028] In the context of the present invention, the hydrophobic block consists of one or more repeating motifs selected from hydrophobic C1-C10 alkyl or aryl methacrylates and their combinations.

[0029] The hydrophobic block may consist of a single monomeric unit, thus forming a homopolymer block, or of several different monomeric units, for example 2, thus forming a block that is itself statistical. Preferably, the hydrophobic block consists of a single monomeric unit.

[0030] An alkyl or aryl methacrylate is said to be "hydrophobic" when it is devoid of functions having an affinity with water such as carboxylates, sulfates, alcohols, polyoxyethylenated chains, quaternary ammoniums, etc.

[0031] Preferably, the hydrophobic block may comprise one or more repeating motifs selected from the group consisting of linear, branched or cyclic alkyl methacrylates having from 1 to 10 carbon atoms or aryl methacrylates.

[0032] Preferably, the hydrophobic block comprises one or more repeating motifs selected from methyl methacrylate (MMA) and butyl methacrylate (BMA), 2-ethylhexyl methacrylate, benzyl methacrylate.

[0033] Preferably, the hydrophobic block comprises, in particular is made of, a polymer chosen from poly(butylmethacrylate) (PBMA), poly(methylmethacrylate) (PMMA), most preferably poly(butylmethacrylate).

[0034] According to one or more embodiments, the hydrophobic methacrylic block has an average number-average molar mass (Mn) between 4000 and 30000 g / mol. According to one or more embodiments, the hydrophobic methacrylic block has an average number-average molar mass (Mn) between 6000 and 20000 g / mol. HYDROPHY BLOCK

[0035] In the context of the present invention, the hydrophilic block consists of one or more repeating motifs selected from poly(ethylene oxide) methacrylates (MAPEG), 2-hydroxy-3-phenoxypropylacrylate (HPhOPA), 4-tert-butylcyclohexyl acrylate (tBCHA), N-hydroxyethylacrylamide (HEAA), N,N-diethylacrylamide (DEAA) and their combinations.

[0036] The polymer of the hydrophilic block can consist of a single monomeric motif, thus forming a homopolymer block, or of several different monomeric motifs, for example 2, thus forming a statistical block.

[0037] Preferably the repeating motif of the hydrophilic block is uncharged.

[0038] Preferably, the hydrophilic block consists of one or more repeating motifs selected from poly(ethylene oxide) methacrylates, the combination of 2-hydroxy-3-phenoxypropylacrylate and 4-tert-butylcyclohexyl acrylate, the combination of N-hydroxyethylacrylamide and N,N-diethylacrylamide.

[0039] In the context of the present invention, the term poly(ethylene oxide) methacrylates (“MAPEG”) refers to poly(ethylene oxide) methacrylate of linear formula H2C=C(CH3)CO(OCH2CH2)nOH (“MAPEG-OH”) and to poly(ethylene oxide) methacrylate methyl ether of linear formula H2C=CCH3CO2(CH2CH2O)nCH3 (“MAPEG-CH3”). The ns number is generally between 5 and 30.

[0040] According to one or more embodiments, the hydrophilic poly(methacrylic) block has an average number molar mass (Mn) between 5000 and 150000 g / mol.

[0041] The hydrophilic block polymer is not a zwitterionic species. The hydrophilic block polymer is not made up of, and preferably does not comprise, fluorinated monomeric units. AMPHIPHILE BLOCK COPOLYMER

[0042] According to one or more embodiments, the amphiphilic block copolymer comprises at least one block selected from PBMA, PMMA, PDMAEMA, and PDEAEMA. According to one or more embodiments, the amphiphilic block copolymer comprises at least one of the following formulations: PBMA-b-PMAPEG, PBMA-bP(tBCHA-co-HPhOPA), PBMA-bP(HEAA-co-DEAA).

[0043] Generally, the number-average molar mass of the amphiphilic block copolymer may be less than or equal to 500,000 g / mol, preferably between 10,000 and 300,000 g / mol.

[0044] According to one or more embodiments, the amphiphilic block copolymer comprises 20 to 80 mol% (mol%) of hydrophilic repeating motifs.

[0045] According to one or more embodiments, the amphiphilic block copolymer comprises 50 to 80 mol% (mol%) of hydrophilic repeating motifs.

[0046] According to one or more embodiments, the amphiphilic block copolymer comprises from 20 to 80 mol% of hydrophobic repeating units. According to one or more embodiments, the amphiphilic block copolymer comprises from 20 to 50 mol% of hydrophobic repeating units.

[0047] Within the framework of the present invention, the amphiphilic block copolymer can be prepared by controlled polymerization, such as by controlled radical polymerization (reversible addition-fragmentation chain transfer (RAFT), controlled radical polymerization by nitroxides (NMP), etc.).

[0048] Within the framework of the present invention, the polymeric matrix can be of any type provided that good dispersion of the amphiphilic block copolymer can be obtained.

[0049] Preferably, the polymer matrix comprises one or more polymers selected from the group consisting of polyurethane (PU), polyethylene (PE), polyester, glycolized polyester (PETG), alkyl poly(meth)acrylates, polystyrene (PS), polyvinyl chloride (PVC), polypropylene (PP), ethylene vinyl acetate (EVA), acrylonitrile butadiene styrene (ABS), polysiloxanes, polycarbonates (PC), polyamides, polyacetals, polysulfones, polyaryletherketones (PAEK) and their combinations.

[0050] Preferably, the amphiphilic block copolymer is dispersed homogeneously in the matrix.

[0051] In the context of the present invention, the term "homogeneous dispersion" refers to a mixture of ingredients, such as the polymer matrix and the amphiphilic block copolymer, in which the proportions of each ingredient throughout the mixture are identical, in particular the proportions of each ingredient are the same on the surface and in the core of the mixture. In other words, the amphiphilic block copolymer does not accumulate on the surface of the material. Advantageously, obtaining a homogeneous dispersion makes it possible to achieve good non-stick performance, even at a low concentration of amphiphilic block copolymer.

[0052] Within the framework of the present invention, the content of amphiphilic block copolymer in the material is generally greater than or equal to 0.5% by weight and less than or equal to 10% by weight relative to the total weight of the material, preferably less than or equal to 5% by weight, and very preferably less than or equal to 4% by weight.

[0053] According to one embodiment, the content of amphiphilic block copolymer is about 2% by weight relative to the total weight of the material, preferably between 1.8% by weight and 2.2% by weight relative to the total weight of the material. USES

[0054] According to another aspect, the present invention relates to the use of an amphiphilic block copolymer as defined above for the preparation of a material with anti-stick and / or anti-fouling properties. The anti-stick and / or anti-fouling properties of the material, conferred by the amphiphilic block copolymer as defined above, make it possible, in particular, to prevent the adhesion and / or accumulation of dirt such as dust, grease or oily substances, substances present in bodily fluids, such as blood and its derivatives, urine, saliva, juices, sweat, and in particular organic compounds from the protein, lipid or polysaccharide family.

[0055] In particular, the amphiphilic block copolymer as defined above is used for the preparation of a material with anti-stick and / or anti-fouling properties with respect to substances present in bodily fluids, such as blood and its derivatives, urine, saliva, juices, sweat, and in particular organic compounds of the protein, lipid or polysaccharide family.

[0056] Advantageously, the material according to the present invention therefore makes it possible to prevent the accumulation of substances from bodily fluids, such as blood and its derivatives, urine, saliva, juices or sweat, in particular organic compounds from the protein, lipid or polysaccharide family.

[0057] Finally, the present invention relates to the use of the material as defined above for the preparation of an article with non-stick and / or anti-fouling properties. Such an article can be useful in various applications requiring an easy-to-clean surface and where it is desirable to prevent the adhesion and / or accumulation of dirt such as, for example, dust, grease or oily substances, substances present in bodily fluids, such as blood and its derivatives, urine, saliva, juices, sweat, and in particular organic compounds from the protein, lipid or polysaccharide family.

[0058] The article can be chosen from medical devices, packaging, in particular food packaging, containers, furniture, utensils, for example kitchen utensils, filtration membranes, pipes, devices for transporting liquids or biological media (blood bags, nutritional media etc.), textiles, such as for example anti-soiling mats, shoes, clothing, building components, such as for example a door handle, floor coverings, sports facilities, personal protective equipment, preferably from medical devices, packaging, in particular food packaging, containers, furniture, utensils, filtration membranes, pipes, devices for transporting liquids or biological media.

[0059] Advantageously, the article is a medical device, for example a catheter.

[0060] Advantageously, the materials according to the present invention have mechanical properties suitable for their use in the preparation of an article as described above, in particular a medical device, for example a catheter.

[0061] An object of the present invention also relates to an article having non-stick and / or anti-fouling properties such as, in particular, medical devices, packaging, especially food packaging, containers, furniture, utensils, for example kitchen utensils, filtration membranes, pipes, devices for transporting liquids or biological media (blood bags, nutritional media, etc.), textiles, such as anti-soiling mats, shoes, clothing, building components, such as a door handle, floor coverings, sports facilities, personal protective equipment, preferably medical devices, packaging, especially food packaging, containers, furniture, utensils, filtration membranes, pipes, devices for transporting liquids or biological media, comprising a material according to the present invention.

[0062] The present invention also relates to a method for preparing a material according to the present invention.

[0063] Preferably, the process includes a step in which the polymer matrix and the amphiphilic block copolymer are mixed in at least one extruder to obtain a rod of material. The extrusion step can be carried out using one or more extruders. This rod of material is then shaped by extrusion or injection molding.

[0064] Optionally, the extrusion step can be preceded by a compounding step of the polymer matrix and the amphiphilic block copolymer. EXAMPLES

[0065] [Tables 1] Analysis Equipment: ¹H NMR Spectrometer, BRUKER Avance III nanobay - 400MHz; Size Exclusion Chromatography (SEC) Method: THF HLC-8320GPC EcoSEC (Tosoh); Size Exclusion Chromatography (SEC) Method: DMF PL-GPC120 (Agilent); Water Contact Angle Measurement: KRÜSS "EasyDrop" System; Protein Assay by Absorbance Reading on Multi-Well Plates: BioTek Synergy Mx Plate Reader; Gen5 Software; Mechanical Property Measurement: Testometric Tensile Testing Bench, 2.5 kN, M25, 0-2.5 CT

[0066] Example 1: Synthesis and characterization of the PMBA block

[0067] In a suitable reactor, dissolve 1 eq. of AIBN (azobisisobutyronitrile), 5 eq. of RAFT agent 4-cyano-4-(((dodecylthio)carbonothioyl)thio)pentanoic acid, and 386 eq. of BMA in toluene (1 volume of monomer / 1 volume of solvent) and stir until the mixture is completely homogenized. Degas the mixture by bubbling with argon for 30 min. Then heat the mixture to 70°C with stirring (700 rpm) for 8 h. Stop the reaction by transferring the mixture to an ice bath and introducing oxygen. Precipitate the polymer formed in a MeOH / H2O (4:1) mixture twice to remove all residual monomers. Allow the mixture to settle and remove the supernatant before drying under vacuum.

[0068] Characterizations:

[0069] BMA conversion = 83%

[0070] SEC: (THF)

[0071] Mn = 8000 g / mol

[0072] E>=1.43

[0073] Example 2: Synthesis and characterization of an amphiphilic block copolymer PBMA-b-PMAPEG

[0074] In a suitable reactor, dissolve 1 eq. of AIBN, 5 eq. of PBMA, and 930 eq. of PEGMA360 in methyltetrahydrofuran (MeTHF) (1 volume of monomer / 8 volumes of solvent) and stir until the mixture is completely homogenized. Degas the mixture under argon for 30 minutes, then heat the mixture to 70°C with stirring (700 rpm) for 6 hours. Stop the reaction by transferring the mixture to an ice bath and introducing oxygen. Precipitate the polymer formed in cold pentane to obtain a colorless gel.

[0075] Characterizations:

[0076] MAPEG conversion = 62%

[0077] (NMR estimate *H) Mn = 50,000 g / mol

[0078] Example 3: Synthesis and characterization of an amphiphilic block copolymer PBMA-bP(tBCHA-co-HPhOPA)

[0079] In a suitable reactor, dissolve 1 eq. of AIBN, 5 eq. of RAFT PBMA macroinitiator, 258 eq. of tBCHA, and 258 eq. of HPhOPA in a toluene / DMSO (1:1) mixture (1 volume of monomer to 3 volumes of solvent) and stir until the mixture is completely homogenized. Degas the mixture by bubbling with argon for 30 min. Then heat the mixture to 70°C with stirring (700 rpm) for 3 h. Stop the reaction by transferring the mixture to an ice bath and introducing oxygen. Precipitate the polymer formed in cold pentane twice to remove all residual monomers. Allow to settle and remove the supernatant before drying under vacuum.

[0080] Characterizations:

[0081] tBCHA conversion = 99%

[0082] HPhOPA conversion = 99%

[0083] SEC: (DMF)

[0084] Mn = 18400 g / mol

[0085] D=l,5

[0086] Example 4: Synthesis and characterization of an amphiphilic block copolymer PBMA-bP(DEAA-co-HEAA)

[0087] In a suitable reactor, dissolve 1 eq. of AIBN, 5 eq. of RAFT PBMA macroinitiator, 258 eq. of DEAA, and 258 eq. of HEAA in a toluene / DMSO (1:1) mixture (1 volume of monomer to 3 volumes of solvent) and stir until the mixture is completely homogenized. Degas the mixture by bubbling with argon for 30 min. Then heat the mixture to 70°C with stirring (700 rpm) for 3 h. Stop the reaction by transferring the mixture to an ice bath and introducing oxygen. Precipitate the polymer formed in cold pentane twice to remove all residual monomers. Allow the mixture to settle and remove the supernatant before drying under vacuum.

[0088] Characterizations:

[0089] HEAA Conversion = 99%

[0090] DEAA conversion = 99%

[0091] SEC: (DMF)

[0092] Mn = 23200 g / mol

[0093] D=l,2

[0094] Example 5: Synthesis and characterization of a zwitterionic copolymer (PBMA-b-PSBBAm)

[0095] Synthesis of the zwitterionic monomer SBBAm:

[0096] In a suitable reactor, 1.11 eq. of N-(3-(dimethylamino)propyl)acrylamide and 1 eq. of 1,4-butanesultone are solubilized in acetonitrile with BHT (radical scavenging stabilizer), and refluxed for 48 h. A white precipitate is formed, before being filtered, washed with acetonitrile and dried under vacuum.

[0097] Characterizations:

[0098] NMR:

[0099] 'H NMR: ô (D2O) 6.28 (2H, m, CH2=CH-); 5.85 (1H, m, CH2=CH-); 3.43 (6H, m, -NH-CH2- + -CH2-N+-); 3.13 (6H, s, -N+-CH3); 3.02 (2H, m, -CH2-SO3-); 2.09 (2H, m, -NH-CH2-CH2-); 1.97 (2H, m, -N+-CH2-CH2-); 1.85 (2H, m, -CH2-CH2-SO3-)

[0100] In a suitable reactor, solubilize 1 eq. of AIBN, 5 eq. of RAFT PBMA macroprimer and 120 eq. of SBBAm in an equivolume mixture of toluene and trifluoroethanol (3 volumes of mixture to 1 g of monomer). Homogenize under magnetic stirring and degas by bubbling with argon for 30 min. Place the mixture in an oil bath at 70°C and let it react for 48 hours. The polymer formed will have precipitated due to its ionic nature; filter the product and wash it with toluene before drying under vacuum.

[0101] SBBAm conversion = 42%

[0102] % PBMA = 57%

[0103] %P(SBBAm) = 43%

[0104] Example 6: Preparation of materials according to the invention and comparison

[0105] The matrix used is a polyurethane matrix.

[0106] The amphiphilic block copolymers of Examples 2 to 4 and a zwitterionic copolymer PBMA-b-PSBBAm (Example 5) are used to form materials according to the invention (amphiphilic block copolymers of Examples 2 to 4) and comparative (copolymer of Example 5).

[0107] Comparative materials were also prepared: - By direct grafting via transcarbamoylation of polyethylene glycol (PEG) onto a PU (Cl) surface, - By grafting PEG onto PU surfaces via allophanate reaction following the protocol of Brash et al., and using a grafting agent, methylene diphenyl diisocyanate (MDI) (C2), and - By preparing a copolymer having perfluorinated ends of the type CF3-[CF2]n-CH2CH2-O- according to the technology developed by Santerre et al. Allowing to provide a surface hydrophobicity (C3). PHYSICO-CHEMICAL CHARACTERIZATION Measurement of Young's modulus

[0108] The 5A type tensile test specimens required for mechanical testing are produced by injection molding. The polymer granules to be used are first dried at 90°C for 4 hours to remove water and prevent the formation of gas bubbles in the object. The injection nozzle is heated to 200°C to melt the polymer, while the mold is heated to 60°C to cool the formed object. The pressure applied to the polymer during injection is 500 bar to ensure the production of the specimen.

[0109] [Tables2] Example Young's Modulus (MPa) PU + example 2 (2% by weight) 40.3 + 1.04 PU 39.75 + 2.91

[0110] The mechanical properties of materials including the addition of a copolymer are comparable to those of a material without a copolymer. HYDROPHILY TEST

[0111] Water contact angle measurements are performed by image processing. 0.1 mL drops of ultrapure water are deposited on the surfaces being analyzed, and the equipment's camera captures the image. The software allows the contact angle values ​​to be obtained by defining the baseline and the interface between the gas, liquid, and solid phases.

[0112] [Tableaux3] Example Contact Angle PU + example 2 (2% by weight) 77° PU + example 2 (3% by weight) 64° PU + example 2 (4% by weight) 60° PU 87° Cl (grafted PU) 53° C2 (grafted PU) 8°

[0113] The results show that the surface hydrophilicity is increased for a material obtained by dispersing the copolymer according to Example 2 in polyurethane. PROTEIN ADHESION MEASUREMENT

[0114] According to the procedure described by Smith et al. (Analytical Biochemistry 1985, 150, 76-85), analyte films were placed in 6-well plates and washed with ethanol before being stabilized in 5 mL of PBS for 1 h at room temperature with orbital shaking at 450 rpm. The PBS was then removed and replaced with 3 mL of 1 mg / mL bovine serum albumin (BSA) solution, which was left at room temperature for 2 h before being removed. The films were then gently washed with 5 mL of PBS followed by 5 mL of sterile water. 2 mL of 1% wt. SDS solution were then added to each film before placing each 6-well plate in a Branson 1800 ultrasonic bath for 30 min. 100 pL of each solution were then taken and transferred into a 96-well plate.

[0115] A stock solution of BSA was prepared at 50 pg / mL. From this, dilutions were made to obtain the 6 standard solutions at 0, 0.5, 5, 10, 20, and 30 pg / mL, respectively. For each analyte film, 100 pL of each standard were taken and transferred to the corresponding wells.

[0116] The colored indicator is then prepared by mixing two buffer solutions QA and QB and a 4% wt% copper sulfate solution from the QuantiPro™ BCA Assay Kit marketed by Sigma-Aldrich, in a ratio of 25 / 25 / 1 and in The mixture was vortexed. 100 µL of colored indicator was added to each standard solution and each analyte. The 96-well plates were then placed in an oven at 37°C for 2 hours to allow the indicator to react with the proteins. Each plate was then scanned using a BioTek Synergy Mx reader, and the absorbance of each well was measured at 562 nm using Gen5 software.

[0117] [Tables4] Example Protein Adhesion (BSA) (pg / cm3) Reduction in adhesion compared to matrix alone (%) PU + example 2 (2% wt) 1.028+0.112 26.88 PU + example 3 (2% wt) 1.097+0.082 18.28 PU + example 4 (2% wt) 1.051+0.086 23.55 PU + example 5 (2% wt) 1.562+0.101 -17.04 PU 1.292+0.039 - HDPE + example 2 (2% wt) 1.126+0.048 12.72 HDPE + example 3 (2% wt) 1.094+0.069 16.26 HDPE + example 4 (2% wt) 1.147+0.086 11.03 HDPE + example 5 (2%wt) 1.527+0.079 -16.82 HDPE 1.268+0.083 0 LDPE + example 2 (2%wt) 1.633+0.091 8.20 LDPE + example 3 (2%wt) 1.504+0.010 17.67 LDPE + example 4 (2% weight s) 1.689+0.070 4.51 LDPE + example 5 (2% weight s) 2.240+0.332 -19.96 LDPE 1.763+0.195 0 PETG + example 2 (2% weight s) 2.020+0.210 37.29 PETG + example 3 (2% weight) 2.123 + 0.123 30.05 PETG + example 4 (2% weight) 1.654 + 0.201 68.29 PETG + example 5 (2%wt) 2.683+0.159 2.88 PETG 2.754+0.150 0 PMMA + example 2 (2%wt) 1.243+0.015 18.14 PMMA + example 3 (2%wt) 1.361+0.031 7.90 PMMA + example 4 (2%wt) oids) 1.364+0.033 7.70 PMMA + example 5 (2%wt) 2.127+0.351 -29.37 PMMA 1.468+0.111 0 HDPE refers to high-density polyethylene (PE). LDPE refers to low-density polyethylene (PE).

[0118] Regardless of the matrix used, the materials according to the invention are capable of reducing protein adhesion compared to the use of a material not comprising an amphiphilic block copolymer or in which a zwitterion is dispersed.

Claims

Demands

1. Material comprising a polymer matrix in which is dispersed an amphiphilic block copolymer comprising: - a hydrophobic block comprising one or more repeating units selected from hydrophobic C1-C10 alkyl or aryl methacrylates and their combinations, and - a hydrophilic block comprising one or more repeating units selected from poly(ethylene oxide) methacrylates, 2-hydroxy-3-phenoxypropylacrylate, 4-tert-butylcyclohexyl acrylate, N-hydroxyethylacrylamide, N,N-diethylacrylamide, and their combinations.

2. Material according to claim 1 in which the hydrophilic block is uncharged and / or comprising one or more repeating motifs selected from poly(ethylene oxide) methacrylates (MAPEG), 2-hydroxy-3-phenoxypropylacrylate (HPhOPA), 4-tert-butylcyclohexyl acrylate (tBCHA), N-hydroxyethylacrylamide (HEAA), N,N-diethylacrylamide (DEAA) and combinations thereof.

3. Material according to claim 1 or 2, wherein the content of amphiphilic block copolymer in the material is greater than or equal to 0.5% by weight and less than or equal to 10% by weight relative to the total weight of the material.

4. Material according to any one of claims 1 to 3 wherein the amphiphilic block copolymer content in the material is less than or equal to 5% by weight relative to the total weight of the material, preferably less than or equal to 4% by weight.

5. Material according to any one of claims 1 to 4, wherein the hydrophobic block repeating pattern is selected from methyl methacrylate and butyl methacrylate, preferably the hydrophobic block repeating pattern is butyl methacrylate.

6. Material according to any one of claims 1 to 5, wherein the amphiphilic block copolymer is selected from the following copolymers: PBMA-b-PMAPEG, PBMA-bP(tBCHA-co-HPhOPA), PBMA-bP(HEAA-co-DEAA)

7. Material according to any one of claims 1 to 6, wherein the amphiphilic block copolymer has a molar mass number average (Mn) less than or equal to 500,000 g / mol, preferably between 10,000 and 300,000 g / mol.

8. Material according to any one of claims 1 to 7, wherein the polymer matrix comprises one or more polymers selected from the group consisting of polyurethane (PU), polyethylene (PE), polyester, glycolized polyester (PETG), alkyl poly(meth)acrylates, polystyrene (PS), polyvinyl chloride (PVC), polypropylene (PP), ethylene vinyl acetate (EVA), acrylonitrile butadiene styrene (ABS), polysiloxanes, polycarbonates (PC), polyamides, polyacetals, polysulfones, polyaryletherketones (PAEK) and combinations thereof.

9. Material according to any one of claims 1 to 8, wherein the amphiphilic block copolymer is homogeneously dispersed in the matrix.

10. A method for preparing a material as defined in any one of claims 1 to 9 comprising a step in which the polymeric matrix and the amphiphilic block copolymer as defined above are mixed in at least one extruder enabling the production of a rod of material, shaped by extrusion or injection molding.

11. Use of an amphiphilic block copolymer comprising: - a hydrophobic block comprising one or more repeating units selected from hydrophobic C1-C10 alkyl or aryl methacrylates and combinations thereof, and - a hydrophilic block comprising one or more repeating units selected from poly(ethylene oxide) methacrylates, 2-hydroxy-3-phenoxypropylacrylate, 4-tert-butylcyclohexyl acrylate, N-hydroxyethylacrylamide, N,N-diethylacrylamide, and combinations thereof, for the preparation of a material with anti-stick and / or anti-fouling properties.

12. Articles with non-stick and / or anti-fouling properties such as medical devices, packaging, including food packaging, containers, furniture, utensils, for example kitchen utensils, filter membranes, pipes, devices for transporting liquids or biological media (blood bags, nutritional media, etc.), textiles, such as by

13. Examples include anti-fouling mats, shoes, clothing, building components such as door handles, floor coverings, sports facilities, personal protective equipment, preferably medical devices, packaging, including food packaging, containers, furniture, utensils, filtration membranes, pipes, and devices for transporting liquids or biological media, comprising a material as defined in any one of claims 1 to 9. Use of the material as defined in any one of claims 1 to 9 for the preparation of an article with anti-stick and / or anti-fouling properties.

Images