Block copolymer with improved sebum resistance

Abstract

The present invention relates to the use of PCL in the preparation of block copolymers comprising at least one rigid block and at least one flexible block to increase the sebum resistance of the block copolymer. The present invention also provides a sebum-resistant block copolymer comprising a rigid block and a flexible block comprising at least 50% by weight of PCL, with the total weight of the flexible block comprising 100%; a method for synthesizing the copolymer; and compositions and articles comprising such sebum-resistant copolymers.

Description

[Technical Field]

[0001] The present invention relates, in particular, to thermoplastic polymer elastomers (TPEs) and block copolymers having rigid polyamide blocks and flexible blocks that exhibit improved sebum resistance.

[0002] These are of interest for any device that may come into contact with the skin for longer or shorter periods, or repeatedly. [Background technology]

[0003] Thermoplastic resin elastomers constitute a class of materials exhibiting a unique combination of properties. These materials can be formulated to possess both elasticity, flexibility, and strength. Particularly advantageous are that, due to the properties of their thermoplastic resins, these materials can also be processed in a molten state. Furthermore, unlike their cross-linked rubber counterparts, thermoplastic resin elastomers can be recycled and reprocessed.

[0004] Thermoplastic elastomers are used in a wide range of applications. TPE materials, for example, can be molded and overmolded, allowing for the formation of additional layers on existing molded parts. Due to their flexibility and elastic properties, thermoplastic elastomers are commonly used in applications where the material deforms continuously or repeatedly, or in contact with other moving parts.

[0005] Sebum resistance is an important property of thermoplastic resin elastomer compositions used to manufacture articles that come into permanent or repeated contact with the human body, such as handles, buttons, or protective elements for electronic devices, IT and / or telephone communication articles. Repeated contact with sebum can cause staining or discoloration of certain elastomers, as well as loss of mechanical properties and even deformation or swelling. It is well known that human skin secretes sebum, which corrodes polymer chains and reduces molecular weight. Furthermore, artificial sebum may be applied to the skin. This consists of natural and artificial chemicals such as saturated and unsaturated fatty acids, with oleic acid, stearic acid, and palmitic acid being examples.

[0006] Thermoplastic resin elastomer compositions have been found to still be prone to degradation when repeatedly in contact with sebum in certain applications.

[0007] For example, particularly in the electronics market, one of the obstacles to the use of TPE in skin-contact articles is their low resistance to sebum. The cause is the flexible blocks, especially polyether blocks such as PTMG, which are inherently lipophilic. Since these copolymers often have a very high polyether content, the most affected grades are those with flexible blocks, mainly those with block copolymers containing flexible blocks. [Overview of the project]

[0008] Therefore, the object of the present invention is to provide a thermoplastic resin polymer elastomer composition (abbreviated as "TPE") that exhibits improved sebum resistance.

[0009] The applicant has found that using polycaprolactone as the flexible block yields a full range of TPEs that are particularly resistant to sebum. This includes the most flexible grades with a Shore D hardness of less than 50 shD, preferably less than 40 Shore D.

[0010] The TPE obtained in this invention unexpectedly possesses very good tensile mechanical properties—Young's modulus and deformation (elongation) at break (according to ISO standard 527-2:2012-1A)—comparable to TPEs based on flexible polyether blocks, the only difference being that, in the case of the TPE according to this invention, these mechanical properties are retained even after prolonged and / or repeated contact with sebum.

[0011] In fact, beyond a certain level of PCL used in flexible blocks, an improvement in the deformation (elongation) of these TPEs upon severity (measured according to ISO standard 527-2:2012-1A) is observed. [Modes for carrying out the invention]

[0012] Therefore, the present invention provides the use of polycaprolactone (abbreviated as PCL) in preparing a block copolymer having rigid blocks and flexible blocks in order to enhance the sebum resistance of the block copolymer.

[0013] Polycaprolactone is a hydrophobic and biodegradable synthetic aliphatic polyester. This semi-crystalline polymer is non-toxic.

[0014] More specifically, polycaprolactone (PCL) refers to polycaprolactone having two, three, or four functionalities, preferably polyols, and having a number-average molar mass (Mn) in the range of 400 to 10,000 g / mol.

[0015] In the sense of the present invention, polycaprolactone is preferably a polycaprolactone polyol produced by addition polymerization, which involves ring-opening of epsilon-caprolactone with the hydroxyl group of an initiator.

[0016] Caprolactone, more specifically epsilon-caprolactone, is a commercially available lactone. The reaction is carried out at a temperature in the range of 100 to 230°C, preferably in the presence of a catalyst. Patent documents US3021309 and US3021317 describe these types of cyclic ester polymerization reactions. Epsilon-caprolactone may be substituted with 6-hydroxycaproic acid.

[0017] Polyols that can be used as initiators can be represented by the general formula: R-(OH)x [wherein R represents an aromatic hydrocarbon group having one or two aromatic rings, an alicyclic hydrocarbon group having 4 to 37 carbon atoms, a saturated or unsaturated aliphatic group having 1 to 30 carbon atoms, a polyester polyol residue having an average molecular weight of 200 to 6000 g / mol, or a polyalkylene glycol residue having an average molecular weight of 200 to 6000 g / mol, and x represents an integer from 2 to 4.]

[0018] Examples of initiators include resorcinol, pyrocatechol, hydroquinone, pyrogallol, phloroglucinol, bisphenol A, bisphenol F, and addition products of ethylene with these; dimethylolbenzene, cyclohexanedimethanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 2-methyl-1,3-propylene glycol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, glycerol, trimethylolpropane or pentaerythritol; polyester polyols or fatty acid dimers formed from dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, sebacic acid, undecanedioic acid or dodecanedioic acid with an average molecular weight of 200 to 6000 g / mol, and diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol or 1,6-hexanediol; polyethylene glycol, propylene glycol and polytetramethylene glycol with an average molecular weight of 200 to 6000 g / mol; random copolymers or block copolymers of ethylene oxide and propylene oxide; and random copolymers or block copolymers of ethylene oxide and tetrahydrofuran.

[0019] The polycaprolactone polyol preferably contains at least two terminal hydroxyl groups.

[0020] [[ID=⑧]]Preferred initiator polyols are particularly selected from neopentyl glycol, butanediol, diethylene glycol, ethylene glycol, hexanediol, polytetramethylene glycol, fatty acid dimer diol, or polyesters containing at least one fatty acid dimer diol.

[0021] It should be noted that there is an error in the original text. The line "[[ID=⑧]]" should be "" in the original. The above translation has been corrected accordingly.PCL polyols particularly suitable for use in the present invention may also be selected from the CAPA series manufactured by Ingevity or the Priplast XL series manufactured by Croda. Priplast XL is particularly described in Patent Document US2016 / 0229946.

[0022] PCL preferably occupies at least 10% by weight, preferably at least 15% by weight, preferably at least 20% by weight, preferably at least 25% by weight, preferably at least 30% by weight, preferably at least 35% by weight, preferably at least 40% by weight, preferably at least 45% by weight, preferably at least 50% by weight, preferably at least 55% by weight, preferably at least 60% by weight, preferably at least 65% by weight, preferably at least 70% by weight, preferably at least 75% by weight, preferably at least 80% by weight, preferably at least 85% by weight, preferably at least 90% by weight, preferably at least 95% by weight, preferably at least 98% by weight, preferably at least 99% by weight, based on the total weight of the flexible blocks that make up 100%.

[0023] PCL preferably occupies 100% of the flexible blocks.

[0024] PCL advantageously occupies 50 - 100% by weight, preferably 80 - 100% by weight, of the flexible blocks based on the total weight of the flexible blocks that make up 100%. At these ratios, the use of PCL in the copolymer containing the rigid block and the flexible block according to the present invention enhances the sebum resistance of the block copolymer without impairing its tensile mechanical properties.

[0025] According to another particularly advantageous embodiment of the present invention, PCL is: - the sebum resistance of the block copolymer, and - the elongation at break of the copolymer when in contact with sebum Used in copolymers containing rigid and flexible blocks to enhance both, PCL accounts for 50-100% by weight, preferably 80-100% by weight, and preferably 90-100% by weight, of the total weight of the flexible blocks, which account for 100%.

[0026] The present invention also, rigid block, and The flexible block comprises at least 50% by weight of PCL, preferably 50-100% by weight of PCL, preferably 50-90% by weight, preferably more than 50% by weight of PCL, preferably at least 55% by weight of PCL, preferably at least 60% by weight of PCL, preferably at least 65% by weight of PCL, preferably at least 70% by weight, preferably at least 75% by weight, preferably at least 80% by weight, and preferably 80-90% by weight of PCL, relative to the total weight of the flexible block which accounts for 100% of the total weight. , possible We also provide a sebum-resistant block copolymer characterized by containing a flexible block.

[0027] The block copolymer according to the present invention is understood to mean a thermoplastic resin elastomer polymer (TPE), which comprises alternating blocks or segments of “rigid” or “stiff” (with somewhat thermoplastic behavior) and “flexible” or “flexible” (with somewhat elastomeric behavior). A block is said to be “flexible” if it has a low glass transition temperature (Tg). A low glass transition temperature is understood to mean a glass transition temperature Tg of less than 15°C, preferably less than 0°C, advantageously less than -15°C, more advantageously less than -30°C, and possibly less than -50°C.

[0028] Advantageously, the at least one block copolymer comprises at least one block selected from a polyether block, a polyester block, a polyamide block, a polyurethane block, and mixtures thereof.

[0029] The flexible or pliable blocks intended in the copolymers according to the present invention mean, in particular, those comprising, in addition to PCL, at least one of the following polymers: polyethers; polyesters; polysiloxanes such as polydimethylsiloxane i.e., PDMS; polyolefins; polycarbonates; and mixtures thereof. Pliable blocks are described, for example, on pages 32, line 3 to 38, line 23 of French Patent Document FR2941700. The present invention prefers polyethers when the pliable block comprises at least one other polymer in addition to PCL. As an example, polyethers are selected from poly(ethylene glycol) (PEG), poly(1,2-propylene glycol) (PPG), poly(1,3-propylene glycol) (PO3G), poly(tetramethylene glycol) (PTMG), and copolymers or mixtures thereof.

[0030] The rigid blocks in the copolymer according to the present invention may be based on polyamide, polyurethane, polyester, or a mixture of these polymers. These blocks are described in particular in French patent application FR2936803. The rigid blocks are preferably polyamide-based.

[0031] Examples of copolymers having rigid and flexible blocks include (a) copolymers having polyester and polyether blocks (also known as COPE or copolyether ester), (b) copolymers having polyurethane and polyether blocks (also known as TPU, an abbreviation for thermoplastic polyurethane), and (c) copolymers having polyamide and polyether blocks (also known as PEBA or polyether-block-amide in accordance with IUPAC).

[0032] Preferably, the at least one block copolymer (A) comprises a copolymer having a polyamide block and a polyether block (PEBA).

[0033] Polyamide (abbreviated as PA) blocks may include homopolyamides or copolyamides. The polyamide blocks that may be envisioned in the compositions of the present invention are those defined in particular on pages 27, line 18 to 31, line 14 of application FR0,950,637. NF EN ISO standard 1874-1:2011 defines the nomenclature for polyamides.

[0034] The term "monomer" used herein in reference to polyamides should be understood to mean "repeating unit." It should be noted that the repeating unit of polyamides is unique when it consists of a combination of diacids and diamines. The monomers are considered to correspond to equimolar combinations of diamines and diacids, i.e., "diamine-diacid" or "XY" pairs. The rationale for this is that solid diacids or solid diamines are merely structural units that cannot polymerize on their own.

[0035] In the block copolymer according to the present invention, the PA block preferably has a carboxylic acid terminus and is therefore referred to as diacid PA. Thus, the bond between the hard block HB (PA in this specification) and the soft block (SB) is generally an ester bond. Polyamide blocks containing dicarbon chain terminus are produced, for example, by the condensation of a polyamide precursor in the presence of a dicarboxylic acid that restricts the chain.

[0036] Three types of polyamides can be used in the composition of these PA blocks.

[0037] According to the first type, the polyamide block is produced by the condensation of at least one (aliphatic, alicyclic, or aromatic) dicarboxylic acid, more specifically a dicarboxylic acid having 4 to 36 carbon atoms, preferably a dicarboxylic acid having 6 to 18 carbon atoms, and at least one (aliphatic, alicyclic, or aromatic) diamine selected from a diamine having 2 to 36 carbon atoms, preferably a diamine having 6 to 12 carbon atoms.

[0038] Examples of aliphatic diacids include butanediic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, myristic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, octadecanedicarboxylic acid, and dimerized fatty acids.

[0039] An example of an alicyclic diacid is 1,4-cyclohexanedicarboxylic acid.

[0040] Examples of aromatic diacids include terephthalic acid (T), isophthalic acid (I), and sodium, potassium, or lithium salts of 5-sulfoisophthalic acid.

[0041] Examples of aliphatic diamines include tetramethylenediamine, hexamethylenediamine, decamethylene-1,10-diamine, dodecamethylenediamine, and trimethylhexamethylenediamine.

[0042] Examples of alicyclic diamines include isomers of bis(4-aminocyclohexyl)methane (BACM or PACM), bis(3-methyl-4-aminocyclohexyl)methane (BMACM or MACM), and 2,2-bis(3-methyl-4-aminocyclohexyl)propane (BMACP), isophorone diamine (IPDA), 2,6-bis(aminomethyl)norbornane (BAMN), and piperazine (Pip).

[0043] Advantageously, the copolymers according to the invention are PA 44, PA 46, PA 49, PA 410, PA 412, PA 413, PA 414, PA 416, PA 418, PA 436, PA 64, PA 66, PA 69, PA 610, PA 612, PA 613, PA 614, PA 616, PA 618, PA 636, PA 94, PA 96, PA 910, PA 912, PA 913, PA 914, PA 916, PA 918, PA 936, PA 104, PA 106, PA 109, PA 1010, PA 1012, PA 1013, PA 1014, PA 1016, PA 1018, PA 1036, PA The PA comprises 10T, PA 10I, PA BMACM4, PA BMACM6, PA BMACM9, PA BMACM10, PA BMACM12, PA BMACM13, PA BMACM14, PA BMACM16, PA BMACM18, PA BMACM36, PA PACM4, PA PACM6, PA PACM9, PA PACM10, PA PACM12, PA PACM13, PA PACM14, PA PACM16, PA PACM18, PA PACM36, PA Pip4, PA Pip6, PA Pip9, PA Pip10, PA Pip12, PA Pip13, PA Pip14, PA Pip16, PA Pip18 and / or PA Pip36, and at least one PA block based on copolymers thereof.

[0044] According to the second type, the polyamide block is produced by the condensation of one or more alpha,omega-aminocarboxylic acids and / or one or more lactams having 6 to 12 carbon atoms in the presence of a dicarboxylic acid having 4 to 36 carbon atoms.

[0045] Examples of lactams include caprolactam, enantractam, and laurolactam.

[0046] Examples of alpha-omega-aminocarboxylic acids include aminocaproic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.

[0047] Advantageously, the second type of polyamide block is made from polyamide 11, polyamide 12, or polyamide 6.

[0048] According to the third type, the polyamide block is produced by the condensation of at least one monomer of the first type and at least one monomer of the second type. In other words, the polyamide block is produced by the condensation of at least one alpha,omega-aminocarboxylic acid (or lactam) and at least one diamine and dicarboxylic acid.

[0049] In this case, the PA block is, - With one or more aliphatic, alicyclic, or aromatic diamines having X carbon atoms; - With one or more dicarboxylic acids having Y carbon atoms; - With lactam and one or more comonomers {Z} selected from alpha,omega-aminocarboxylic acids having Z carbon atoms; - In the presence of excess diacitates used as chain limiting agents or structural units selected from dicarboxylic acids It is prepared by polycondensation.

[0050] As a chain limiting agent, it is advantageous to use a dicarboxylic acid having Y carbon atoms, which is introduced in excess of the diamine's stoichiometry.

[0051] According to one variant of the copolyamide, in the optional presence of a chain limiting agent, polyamide blocks are produced by the condensation of at least two different alpha,omega-aminocarboxylic acids, or the condensation of at least two different lactams having 6 to 12 carbon atoms, or the condensation of one lactam with one aminocarboxylic acid having less than the same number of carbon atoms.

[0052] Examples of polyamide blocks include those formed from the following polyamides (copolyamides): - PA 6 / 12, where 6 indicates caprolactam and 12 indicates laurolactam. - PA 11 / 12, where 11 represents 11-aminoundecanoic acid and 12 represents laurolactam. - PA 6 / 11, where 6 represents caprolactam and 11 represents 11-aminoundecanoic acid. PA 6 / 6.6, where - 6 indicates a caprolactam and 6.6 indicates a monomer produced by the condensation of hexamethylenediamine and adipic acid.

[0053] Further examples include PA 1010 / 11, PA 610 / 11, PA 1012 / 11, PA 1010 / 11 / 12, PA 610 / 1010 / 11, PA 610 / 612 / 11, PA 610 / 612 / 1010, PA 11 / 636, PA 11 / 1036, and PA 1010 / 1036.

[0054] Examples of preferred polyamide blocks in the present invention include those containing at least one of the following molecules: PA12, PA11, PA1010, PA610, PA6, PA6 / 12, and / or those containing at least one of the following monomers: 6, 11, 12, 11, 54, 59, 510, 512, 513, 514, 516, 518, 536, 64, 69, 610, 612, 613, 614, 616, 618, 636, 104, 109, 1010, 1012, 1013, 1014, 1016, 1018, 1036, 10T, 124, 129, 1210, 1212, 1213, 1214, 1216, 1218, 1236, 12T, as well as mixtures thereof or copolyamides.

[0055] The number-average molar mass Mn of the polyamide block is preferably in the range of 400 to 20,000 g / mol, preferably 500 to 10,000 g / mol, and more preferably 600 to 5,000 g / mol.

[0056] The flexible or soft blocks intended in the TPE according to the present invention particularly mean those selected from polyether blocks, polyester blocks, polysiloxane blocks such as polydimethylsiloxane (PDMS) blocks, polyolefin blocks, polycarbonate blocks, and mixtures thereof. The flexible blocks preferably include polyether blocks.

[0057] In the sense of the present invention, a polyether (hereinafter abbreviated as PE) block is understood to mean a polyoxyalkylene such as polyalkylene ether polyols, and especially polyalkylene ether diols. The copolymer PE block of the present invention comprises at least one molecule selected from poly(ethylene glycol) (PEG), poly(1,2-propylene glycol) (PPG), polytetramethylene glycol (PTMG), polyhexamethylene glycol, poly(1,3-propylene glycol) (PO3G), poly(3-alkyltetrahydrofuran), especially poly(3-methyltetrahydrofuran (poly(3MeTHF))), and mixtures thereof. It is also possible to contemplate alternating, random, or block "copolyether" type PE blocks comprising chains of at least two of the above types of PE.

[0058] Polyether blocks may also include blocks obtained by ethoxylation of bisphenols, such as bisphenol A. These latter products are described in patent EP613919.

[0059] Polyether blocks may also contain ethoxylated primary amines. An example of an ethoxylated primary amine is shown below: TIFF0007864487000001.tif36170[In the formula, m and n are between 1 and 20, and x is between 8 and 18.] These products are examples of products sold under the Noramox® brand by CECA and the Genamin® brand by Clariant.

[0060] Block SB preferably contains PTMG in addition to PCL.

[0061] In the sense of the present invention, a polyester block (hereinafter abbreviated as PES) is generally understood to mean a polyester produced by polycondensation between a dicarboxylic acid and a diol. Suitable carboxylic acids include those mentioned above used to form polyamide blocks, with the exception of aromatic acids such as terephthalic acid and isophthalic acid. Suitable diols include linear aliphatic diols, such as branched diols like ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, and neopentyl glycol, as well as cyclic diols such as 3-methylpentane glycol, 1,2-propylene glycol, and 1,4-bis(hydroxymethyl)cyclohexane, and 1,4-cyclohexanedimethanol.

[0062] The term "polyester" also refers to fatty acid dimer-based PES, more specifically, the Priplast® series of products manufactured by Croda, or the Nouracid® series of products manufactured by Oleon.

[0063] It is also possible to consider alternating, statistical, or block "copolyester" type PES blocks containing chains of at least two of the above types of PES.

[0064] For the purposes of the present invention, a polysiloxane (hereinafter abbreviated as PSi) block is understood to mean any organosilicon polymer or oligomer having a linear or cyclic, branched or crosslinked structure, essentially consisting of a main unit (siloxane bond -Si-O-Si-) in which silicon atoms are bonded to each other via oxygen atoms, and a repeating thereof of optionally substituted hydrocarbon groups directly bonded to the silicon atoms via carbon atoms. The most common hydrocarbon groups are alkyl groups, especially C1-C10 groups, and especially methyl, fluoroalkyl groups, aryl groups, and especially phenyl, as well as alkenyl groups and especially vinyl; other types of groups that can be attached to the siloxane chain, either directly or via hydrocarbon groups, are especially hydrogen, halogens, and especially chlorine, bromine or fluorine, thiols, alkoxy groups, polyoxyalkylene (or polyether) groups, and especially polyoxyethylene and / or polyoxypropylene, hydroxyl or hydroxyalkyl groups, substituted or unsubstituted amine groups, amide groups, acyloxy or acyloxyalkyl groups, hydroxyalkylamino or aminoalkyl groups, quaternary ammonium groups, amphoteric or betaine groups, anionic groups, e.g., carboxylates, thioglycolates, sulfosuccinates, thiosulfates, phosphates and sulfates, and mixtures thereof, and of course this enumeration is by no means exhaustive ("organically modified" silicones).

[0065] Preferably, the polysiloxane block comprises polydimethylsiloxane (hereinafter abbreviated as PDMS block), polymethylphenylsiloxane, and / or polyvinylsiloxane.

[0066] For the purposes of this invention, the term polyolefin (hereinafter abbreviated as PO) block means any polymer containing an alpha-olefin as a monomer, i.e., an olefin homopolymer or a copolymer of at least one alpha-olefin and at least one other copolymerizable monomer, wherein the alpha-olefin advantageously has 2 to 30 carbon atoms.

[0067] Examples of alpha-olefins include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene, 1-tetracosene, 1-hexacocene, 1-octacosene, and 1-triacontene. These alpha-olefins may be used individually or as a mixture of two or more.

[0068] For example, - Ethylene homopolymers and copolymers, particularly low-density polyethylene (LDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), and polyethylene obtained by metallocene catalysts. - Propylene homopolymers and copolymers, - Essentially amorphous or atactic poly-α-olefin (APAO), - Ethylene / α-olefin copolymers, such as ethylene / propylene, EPR (ethylene-propylene-rubber) elastomers and EPDM (ethylene-propylene-diene) elastomers, and mixtures of polyethylene with EPR or EPDM. - Styrene / ethylene-butene / styrene (SEBS), styrene / butadiene / styrene (SBS), styrene / isoprene / styrene (SIS), and styrene / ethylene-propylene / styrene (SEPS) block copolymers; - Copolymers of ethylene with at least one product selected from salts or esters of unsaturated carboxylic acids, e.g., alkyl(meth)acrylates where the alkyl can contain up to 24 carbon atoms, vinyl esters of saturated carboxylic acids, e.g., vinyl acetate or propionate, and dienes, e.g., 1,4-hexadiene or polybutadiene. These are some examples.

[0069] According to an advantageous embodiment of the present invention, the at least one polyolefin block comprises polyisobutylene and / or polybutadiene.

[0070] In one particularly advantageous embodiment, the block copolymer according to the present invention comprises at least one flexible polyolefin block (PO block) and at least one hydrophilic rigid block (hereinafter abbreviated as hHB) containing both polyamide and polyether, such as a polyetheramide block, a polyether esteramide block and / or a polyetheramide imide block. The PO block preferably contains a polyolefin containing an acid, alcohol, or amine-terminated group. Preferably, the PO block is obtained by thermally decomposing a high molecular weight polyolefin to form a functionalized polyolefin at a lower mass (reference method: Japanese Patent Application Publication No. 03-62804). The hHB block may also include at least one polymer selected from quaternary amine type and / or phosphorus derivative cationic polymers; and / or modified diacid type anionic polymers containing sulfonate groups that can react with polyols. The addition of an organic salt may then be considered in the preparation of the hHB block or during the reaction between the PO block and the hHB block. US6552131 describes the synthesis of copolymers containing PO blocks and hHB blocks and various possible structures, the latter of which can naturally be assumed in the method according to the present invention.

[0071] For the purposes of this invention, the term polycarbonate block (hereinafter abbreviated as PC block) more specifically means any aliphatic polycarbonate. Aliphatic polycarbonates are described, for example, in DE2546534 and JP1009225. Such homopolymers or copolymers of polycarbonates are also described in document US471203. Patent applications WO92 / 22600 and WO95 / 12629 also describe a method for synthesizing a copolymer containing a polycarbonate block. The blocks (and their synthesis) described in these documents can be fully intended for the synthesis of the PC block copolymer according to the present invention. Preferably, the polycarbonate block of the copolymer according to the present invention is given by the following formula: TIFF0007864487000002.tif31170[wherein a is an integer between 2 and 300; R1 and R2, which may be the same or different, represent a linear or branched aliphatic or alicyclic chain containing 2 to 18 carbon atoms, or represent a polyoxyalkylene group, or represent a polyester group.]

[0072] A polycarbonate is preferred in which R1 and R2 are selected from hexylene, decylene, dodecylene, 1,4-cyclohexylene, 2,2-dimethyl-1,3-propylene, 2,5-dimethyl-2,5-hexylene, or polyoxyethylene groups.

[0073] If the block copolymer described above comprises, in whole, at least one rigid polyamide block and at least one flexible block, then it is clear that the present invention actually comprises all copolymers comprising two, three, four (or more) different blocks selected from the blocks described herein, provided that at least one flexible block containing PCL and at least one rigid block are present. In the copolymer according to the present invention, advantageously, the flexible block (FB) comprises, in addition to PCL, at least one of the following polymers: polyethers; polyesters; polysiloxanes such as polydimethylsiloxanes; polyolefins; polycarbonates; and mixtures thereof, in a small weight ratio (less than 50% by weight) relative to the total weight of the flexible block.

[0074] The flexible block preferably contains a polyether.

[0075] As a result of these ratios in the flexible block, the copolymer according to the present invention is resistant to sebum and also exhibits very good tensile mechanical properties (Young's modulus and deformation at break) that are retained even after prolonged / repeated contact with sebum.

[0076] Advantageously, the copolymer according to the present invention comprises a segmented block copolymer comprising three different types of blocks (referred to herein as “triblocks”), which are resulting from the condensation of at least one PCL block, at least one (other) flexible block and at least one rigid block, as defined above.

[0077] Both rigid and flexible blocks may, advantageously, be derived from renewable and / or fossil-derived materials. The rigid and / or flexible blocks may, advantageously, be derived from at least partially renewable materials. According to one particularly advantageous embodiment of the present invention, polyamide blocks and / or polyether blocks and / or polyester blocks and / or polysiloxane blocks and / or polyolefin blocks and / or polycarbonate blocks may be derived from fully renewable materials.

[0078] Materials of renewable origin, also known as biomaterials, are organic materials from which carbon is produced from CO2 newly fixed (on a human timescale) through photosynthesis from the atmosphere. On land, this CO2 is captured or fixed by plants. In the ocean, CO2 is captured or fixed by bacteria or plankton, leading to photosynthesis. Biomaterials (100% naturally occurring carbon) are 10 -12 Super 14 C / 12 It has a 1.2 × 10¹¹ C isotope ratio, typically 1.2 × 10� -12 To a certain extent, however, fossil materials have a zero ratio. This is because 14 This is because 14C isotopes are formed in the atmosphere and then incorporated into photosynthesis within a timescale of less than several decades. 14 The half-life of C is 5730 years. Therefore, materials derived from photosynthesis, i.e., plants in general, are necessarily isotopes. 14 It has the highest content of C.

[0079] The biogenic content or bio-carbon content is determined by the application of ASTM Standard D 6866 (ASTM Standard D 6866-06) and ASTM Standard D 7026 (ASTM Standard D 7026-04). ASTM Standard D 6866 is entitled "Determining the Biobased Content of Natural Range Materials Using Radiocarbon and Isotope Ratio Mass Spectrometry Analysis", while ASTM Standard D 7026 is entitled "Sampling and Reporting of Results for Determination of Biobased Content of Materials via Carbon Isotope Analysis". The second standard refers to the first standard in the first paragraph.

[0080] The first standard describes a test that measures the 14 C / 12 C ratio of a sample and determines the relative proportion of C of renewable origin in the sample by comparing it with the 14 C / 12 C ratio of a reference sample of 100% renewable origin. This standard is based on the same concept as 14 C dating but does not apply the dating equation.

[0081] The ratio calculated in this way is called "pMC" (percent Modern Carbon). If the material under analysis is a mixture of biogenic material and fossil material (without radioisotopes), the resulting pMC value is directly correlated with the amount of biogenic material present in the sample. 14The reference values ​​used for 14C dating begin in the 1950s. This year was chosen to account for the presence of atmospheric nuclear tests that introduced large amounts of isotopes into the atmosphere after this year. The 1950 reference corresponds to a pMC value of 100. Due to thermonuclear tests, the current value retained is approximately 107.5 (corresponding to a correction value of 0.93). Therefore, the current radiocarbon signature of plants is 107.5. Thus, the signatures of 54 pMC and 99 pMC correspond to the amounts of biomaterial in 50% and 93% of the sample, respectively.

[0082] ASTM standard D 6866 is, 14 Three methods for measuring C isotope content are proposed: - LSC (Liquid Scintillation Count) Spectrometry. This method is, 14 This counts the "beta" particles produced by the decay of carbon. Beta irradiation from a sample of known mass (a known number of carbon atoms) is measured for a specific time. This "radioactivity" is... 14 It is proportional to the number of C atoms, and therefore can be calculated. 14 C emits β-irradiation, which generates photons when it comes into contact with a liquid flashing material (scintillator). These photons have different energies (between 0 and 156 keV), and are known as 14 A 1C spectrum is formed. According to two variants of this method, the analysis relates to either CO2 pre-generated by the carbon-containing sample in a suitable absorption solution, or benzene after the carbon-containing sample has been pre-converted to benzene. Thus, ASTM standard D 6866 provides two methods, A and C, based on this LSC method. - AMS / IRMS (Accelerated Mass Spectrometry combined with Isotope Radioactive Mass Spectrometry). This method is based on mass analysis. The sample is reduced to graphite or CO2 gas and analyzed with a mass spectrometer. This method uses an accelerator and a mass spectrometer, 14 C 12 The ion is separated from the carbon ion, and the ratio of the two isotopes is determined.

[0083] The copolymer according to the present invention is derived at least partially from a biomaterial, and therefore contains at least 1.2 × 10⁻¹⁴ of material. -14 of 14 It contains at least 1% biomaterial, corresponding to the C content.

[0084] The present invention also provides a method for synthesizing a block copolymer according to the present invention, comprising polycondensation of at least one rigid block, in particular a polyamide, with at least one flexible block composed mainly of PCL, i.e., containing more than 50% by weight of PCL relative to the total weight of the flexible block.

[0085] The thermoplastic resin elastomer for the purpose of the present invention is given by the following general formula: -[HB-SB]n- [In the formula, • HB, or rigid block, refers to a block containing polyamide (homopolyamide or copolyamide), polyurethane, polyester, or a mixture of these blocks, preferably polyamide, and will be abbreviated as HB block below; • SB, or soft block, represents a block based on polycaprolactone (PCL) and any other polymer with a low glass transition temperature, such as polyether (PE block), polyester (PES block), polydimethylsiloxane (PDMS block), polyolefin (PO block), polycarbonate (PC block), and / or mixtures of these in the form of alternating, random, or block copolymers. Preferably, the SB is a block that is entirely or partially based on a polyether containing ethylene oxide units. • n represents the number of repeating units of the copolymer unit -HB-SB-. n is in the range of 1 to 60, preferably 5 to 30, or better, even more preferably 6 to 20. This is a block copolymer containing alternating arrangements of hard blocks (HB) and soft blocks (SB).

[0086] The method for synthesizing the block copolymer according to the present invention uses any means to bond the hard block HB to the soft block SB, more specifically to PCL. Several means are possible, such as in solution, in solid state, via interfacial methods, or by a combination of several of these methods, as described in Chapter 9 of the Handbook of Condensation Thermoplastic Elastomers (edited by Stoyko Fakirox, Wiley-VCH, Weinheim, 2005).

[0087] The TPE based on the rigid block and flexible block according to the present invention is produced by bulk polycondensation of a rigid block (HB) having reactive ends and a soft block (SB) having complementary reactive ends, for example, an HB having isocyanate or carboxylic acid chain ends and an SB having alcohol chain ends.

[0088] For example, PEBA-PCL, a copolymer of PA, PE, and PCL blocks, is a PEBA with improved sebum resistance according to the present invention, and is produced by polycondensation of a polyamide block HB having carboxylic acid chain ends and a polyether block SB and PCL block having alcohol chain ends.

[0089] In industry, the method of combining HB with SB is carried out in either two main processes or a single main process.

[0090] Whether in one-step or two-step operations, it is advantageous to operate in the presence of a catalyst. The catalyst is any product that promotes the bonding of polyamide blocks and soft blocks, particularly by esterification. The esterification catalyst is advantageously a derivative of a metal selected from the group formed by titanium, zirconium, and hafnium, or by a strong acid such as phosphoric acid or boric acid. Catalysts described in the following patents may be used: US4,331,786, US4,115,475, US4,195,015, US4,839,441, US4,864,014, US4,230,838 and US4,332,920, WO04,037898, EP1262527, EP1270211, EP1136512, EP1046675, EP1057870, EP1155065, EP506495 and EP504058.

[0091] In the first embodiment, the method of the present invention comprises two main steps. In the first step (I), at least one hard block HB (e.g., PA) is prepared, and in the second step (II), the at least one hard block HB (e.g., PA) is reacted with at least one block SB, preferably in the presence of a catalyst and under reduced pressure.

[0092] Step (I) may include any means known to those skilled in the art for producing a polyamide block, for example, by a polycondensation reaction between a polyamide precursor and a dicarboxylic acid or diamine as a chain control factor. In this case, step I is divided into several substeps: (I-1) A mixture containing at least one PA precursor and at least one chain control factor, such as a diacid, is placed in a reactor (e.g., an autoclave). The chain regulatory factor is preferably selected from adipic acid, sebacic acid, terephthalic acid, isophthalic acid, and mixtures thereof. (I-2) A step of heating the mixture to a temperature within the range of 180 to 350°C, preferably 200 to 300°C, preferably 230 to 290°C. In some cases, water can be added to the mixture to improve heat conduction and / or, in particular, to reach a pressure sufficient for ring opening of lactam 12. (I-3) A high-temperature isothermal step in which the temperature of the mixture is kept constant for a sufficient time to bring all the materials introduced in I-1 into a fluid state, i.e., a state of low viscosity sufficient to contain a homogeneous mixture, and this temperature is in the range of 180-350°C, preferably 200-300°C, preferably 230-290°C. The duration of the high-temperature isothermal stage is generally within the range of 15 minutes to 5 hours, preferably 30 minutes to 4 hours, and preferably 30 minutes to 3 hours. During this high-temperature isothermal stage, pressures develop within the reactor, for example, between 1 and 40 bar. The pressure preferably does not exceed 30 bar, but this maximum pressure depends on the reactor and how it is constructed. (I-4) A step in which water is removed, during which the mixture returns to atmospheric pressure, by expansion of the mixture (decrease in pressure), and / or by distillation. This is water that may be added between steps I-1, I-2, and / or I-3, or water that is formed between these steps; then, (I-5) Purge the mixture with an inert gas in the form of a polyamide block until polymerization is complete. The purging time may be within the range of several minutes to several hours, preferably 5 minutes to 5 hours, preferably 30 minutes to 3 hours, and preferably 1 hour to 2 hours.

[0093] Process I may further include one or more of the following sub-processes: (I-6) Any step to increase the polymerization yield as needed, by maintaining the pressure under reduced pressure, for example, less than 500 mbar, preferably less than 100 mbar. (I-7) Any step of recovering the hard block HB, for example, the PA block.

[0094] All the starting materials necessary for forming the HB block can be loaded into the reactor at the start in an order that a person skilled in the art would consider appropriate, for example, in step I-1 of the method described above. However, it is certainly possible to consider introducing one or more starting materials during any of the sub-steps I-1 to I-7.

[0095] The temperature of this main step I is in the range of 180 to 350°C, preferably 200 to 300°C, or even better, 230 to 290°C.

[0096] The at least one hard block HB (e.g., PA block) may be extruded for subsequent use, stored in the reactor, or transferred to another reactor for carrying out step II as described below.

[0097] Process (II) includes the following sub-processes: (II-1) In the reactor, at least a portion of the amount of at least one soft block SB is brought into contact with the HB block formed in step I, and if necessary, the temperature of the resulting mixture is adjusted to be within the range of 180-350°C, preferably 200-300°C, preferably 200-260°C; (II-2) Any step of purging with nitrogen (or another inert gas) and / or under a slightly reduced pressure, e.g., less than 500 mbar, preferably less than 100 mbar, in order to remove water formed in the reactor during copolymerization; (II-3) Any step of appropriately introducing the remaining portion of at least one block SB.

[0098] The temperature and duration of each step can be easily adjusted by those skilled in the art to optimize the polycondensation reaction while minimizing side reactions. The temperature of this main step II is similarly in the range of 180 to 350°C, preferably 200 to 300°C, or better, even further, 200 to 260°C.

[0099] In a second embodiment, the method of the present invention comprises a single main step, characterized in that the at least one soft block is directly introduced during main step I, i.e., during any of the intermediates I-1 to I-7, similar to the starting materials required for forming a hard block (e.g., a PA block). In this embodiment, main steps I and II are actually performed simultaneously, thus saving time, whereas in the two-main-step embodiment, steps I and II are performed sequentially.

[0100] However, the method of the present invention is preferably a two-step method according to the first embodiment, because a one-step method carries the risk of causing numerous side reactions such as transesterification and / or transesterification / amidation.

[0101] Regardless of these embodiments (one-step or two-step), the method of the present invention includes a final step III for completing and recovering the block copolymer. This step III includes at least two substeps: (III-1) Adjust the viscosity of the obtained copolymer: Reduce the pressure in the reactor under high vacuum until the desired viscosity, i.e., the desired molar mass of the copolymer, is achieved. The “desired molar mass” is understood to mean the number-average molar mass in the range of 10,000 to 100,000 g / mol, preferably in the range of 15,000 to 50,000 g / mol, and preferably in the range of 20,000 g / mol to 40,000 g / mol. The pressure during this sub-step is preferably less than 100 mbar, preferably less than 50 mbar, preferably less than 10 mbar, and more preferably less than 1 mbar. The increase in the molar mass of the copolymer, and therefore the increase in the viscosity of the medium, can be determined, for example, by measuring the change in the torque value that the molten polymer exerts on the stirrer, or by measuring the power consumed by the stirrer at a given stirring speed. (III-2) For example, extrude and recover the block copolymer in the form of pellets or any other form. (III-3) An optional step of baking the pellets to reduce the residual moisture content to less than 0.1% by weight.

[0102] The stirring speed for each step is optimized according to the rheology of the medium and the properties of the stirrer.

[0103] The pressure can be reduced gradually or in stages. The maximum degree of pressure reduction depends on the properties of the chemical species present, their hydrophilicity or hydrophobicity, and their reactivity.

[0104] For catalysts that are readily reactive to hydrolysis, the catalyst may be added during one of steps I and / or II, preferably during one of sub-step II.

[0105] The present invention further provides a sebum-resistant polymer composition characterized by comprising at least one block copolymer according to the present invention as defined above, diluted with a thermoplastic polymer matrix. The polymer matrix advantageously comprises at least one homopolymer or copolymer thermoplastic polymer selected from polyolefins, polyamides, fluoropolymers, saturated polyesters, polycarbonates, styrene resins, PMMAs, thermoplastic polyurethanes (TPUs), ethylene-vinyl acetate copolymers (EVA), copolymers having polyamide blocks and polyether blocks, copolymers having polyester blocks and polyether blocks, copolymers having polyamide blocks, polyether blocks, and polyester blocks, copolymers of ethylene and alkyl (meth)acrylates, copolymers of ethylene and vinyl alcohol (EVOH), ABS, SAN, ASA, polyacetals, polyketones, and mixtures thereof. The composition preferably comprises 1 to 99% by weight, preferably 1 to 40% by weight, of the copolymer and 1 to 99% by weight, preferably 60 to 99% by weight, of the matrix polymer, based on the total weight of the composition accounting for 100%.

[0106] The copolymer according to the present invention may be enriched with stabilizers, plasticizers, lubricants, natural or organic fillers, dyes, pigments, pearlescent materials, antimicrobial agents, flame retardants, antistatic agents, agents that modify the viscosity of the copolymer, and / or any other additives or adjuvants that have already been cited and are well known to those skilled in the art of thermoplastic polymers.

[0107] The present invention further provides articles obtained by injection molding, overmolding, extrusion, co-extrusion, hot compression molding or multi-shot injection molding from at least one copolymer or composition according to the present invention.

[0108] The present invention further provides articles obtained by 3D printing from a copolymer powder or a composition powder according to the present invention.

[0109] Articles obtained from the composition according to the present invention have, advantageously, a tensile modulus of less than 500 MPa, preferably in the range of 10 to 200 MPa, and preferably 20 to 100 MPa, as measured in accordance with ISO standard 527-2:2012-1A.

[0110] The present invention relates to any article that comes into contact with the skin or may come into repeated contact with the skin.

[0111] The present invention is particularly characterized by the following: - Footwear articles or article elements, especially sports footwear, soles, especially insoles, midsole or outsole of sports footwear, or ski boots; - Sports items or elements of items, such as rackets, balls, or floats; - Articles or elements of clothing, accessories or elements of accessories, or articles or elements of personal protective equipment, such as gloves, helmets, life vests, or backpacks; - Optical articles or article elements: components of eyeglass frames, nose pads or nosepieces, protective elements of frames; - Articles or article elements for automobiles, rails, or aircraft: interior decoration elements, rail feet, tires, wheels, steering wheels, seat elements, child car seat components; - Structural, padding, or damping articles or article elements, especially components for damping shocks and / or vibrations such as those caused by means of transport, carpets, sports mats, sports floors or ground coverings, underlays, membranes, handles, especially door handles; - Articles or article elements for childcare, toys, or parts for strollers, prams, or baby carriers; - Medical articles or article elements: patches, drug delivery systems, sensors, splints, orthoses, neck braces, dressings, especially antimicrobial foam dressings; - Electrical and / or electronic articles or article elements: headsets, earphones, Bluetooth® accessories or watches, display screens, connected watches, connected glasses, interactive game components or devices, GPS, connected footwear, bioactivity monitors or sensors, interactive belts or bracelets, trackers, pocket scanners or palm tops, position sensors, visual aids, audio equipment components, thermal insulation and / or soundproofing components; To provide.

[0112] The copolymer according to the present invention is of particular interest in the field of mass-market electrical and electronic equipment (hereinafter "E&E") such as connected bracelets, shells, or external casings for IT, audio, or mobile phone devices.

[0113] Accordingly, the present invention further provides an electrical or electronic article comprising a casing or protective casing manufactured from the copolymer or composition according to the present invention, wherein the article is preferably a portable computer, a mobile phone, or a tablet. [Examples]

[0114] Sebum resistance tests were performed on the following TPE samples. - Cp1: PA12 / PTMG, their respective molar masses are 600 / 2000. - Cp2: PA12 / PTMG, 850 / 2000 - Ex1: PA12 / PCL, 600 / 2000 - Ex2: PA12 / PCL-PTMG-PCL, 600 / 2000, PCL-PTMG-PCL triblock, each with its respective molar mass Includes 500-1000-500 - Cp3:PA11 / PTMG(850 / 2000) - Ex3: PA11 / PCL-PTMG-PCL, 850 / 2000, laboratory sample - Ex4: PA11 / PCL-PTMG-PCL, 850 / 2000, pilot plant sample - Ex5: PA11 / PCL and fatty acid dimer-based polyester, 850 / 2000, polyester containing 82% PCL and 18% fatty acid dimer (18% renewable C). - Ex6: PA11 / PCL and fatty acid dimer-based polyester, 850 / 3000, polyester containing 90% PCL and 10% fatty acid dimer - Ex7: PA11 / PCL, 850 / 2000, laboratory sample - Ex8: PA11 / PCL, 850 / 2000, pilot plant sample - Ex9:PA11 / PCL-PTMG-PCL, 850 / 3000, PCL-PTMG-PCL triblock, containing molar masses of 500-2000-500, laboratory sample

[0115] The chain transfer agent used in all tests is adipic acid.

[0116] Sebum resistance test The sebum used is synthetic sebum supplied by Interchim.

[0117] In the case of Table 1 below, the sample is a small plate measuring 100 x 100 x 2 mm. Cut the 100 x 100 x 2 mm plate into four pieces, place them in a Petri dish, and cover with liquefied sebum at 60°C.

[0118] In the case of Table 2 below, the sample is a dumbbell injection-molded with μ-DSM: Apply the same amount of synthetic liquefied sebum (approximately 0.13 g) to an effective area of ​​the test specimen at 60°C.

[0119] In all cases, the same predetermined amount of sebum is spread on the surface of the sample and removed after conditioning. This procedure is repeated for each sample using three small plates or dumbbells.

[0120] Sebum resistance is measured after conditioning in an oven at 23°C and 50% RH for 7 days. After washing, the thus exposed samples are weighed, and the "mass gain," or weight increase (%), of the sample during testing is calculated. Any visual changes are also recorded.

[0121] In the case shown in Table 2, dumbbells not exposed to sebum were conditioned in an oven at 23°C and 50% RH for 7 days. These controls allowed us to evaluate the minimal effect of moisture gain in copolymers on their weight increase (%).

[0122] Table 1 below shows the various weight gains after 5 and 7 days of exposure. TIFF0007864487000003.tif38170

[0123] Note that, in the case of PA12-based block copolymers in Table 1 above, the maximum mass gain of 14-17% is achieved by PEBA based on a flexible PTMG polyether block. Note that the more polyether-rich the PEBA is (proportionate to the polyamide), the more sebum it absorbs (the weight increase of Cp1 is greater than the weight increase of Cp2). Completely replacing the flexible block with polycaprolactone (Ex1) significantly reduces sebum absorption (weight increase of 4.7% after 7 days of exposure). Partial replacement based on the PCL-PTMG-PCL triblock (with molar masses of 500-1000-500 respectively) in Ex2 also improves the sebum resistance of PEBA (weight increase of 12.3% after 7 days of exposure). TIFF0007864487000004.tif57170

[0124] Note that in the case of PA11-based block copolymers in Table 2 above, the maximum mass acquisition is achieved with the PTMG-based grade (Cp3). All other samples containing PCL show sebum absorption of less than 5.3%. Complete replacement of the flexible block with PCL significantly reduces sebum mass acquisition (by one-third) (for Ex7 and Ex8, absorption decreases to 1.7-1.8%). With partial substitution, for example Ex3 and Ex4, at least 50% PCL relative to the total weight of the flexible block reduces sebum absorption to 3.3-3.5%. Flexible blocks of polyester based on PCL and fatty acid dimers (Ex5 and Ex6) can significantly reduce sebum absorption (at least half compared to Cp3). The best result obtained with Ex6 (Ex6: 2.1% mass obtained compared to 2.6% for Ex5) is due not only to a higher PCL content (90% compared to 82%) but also to a higher molar mass (M for Ex6 compared to 2000 g / mol for Ex5). n This can also be explained by the fact that the copolymer of Ex6 (=3000g / mol) is richer in flexible blocks (78%) than the copolymer of Ex5 (70%).

[0125] mechanical properties The mechanical properties of the PA11-based block copolymer samples shown in Table 2 above were characterized by tensile tests before and after exposure to sebum. Table 3 below summarizes the Young's modulus (MPa) and deformation (elongation) εR (%) at break, measured in accordance with ISO standard 527-2:2012-1A. From this, it is clear that the richer the copolymer is in PCL, the more the mechanical properties of the material are retained after exposure to sebum. Conversely, in the case of the PTMG-based copolymer Cp3, sebum absorption adversely affected the tensile strength: a 25% decrease in modulus and a nearly 100% decrease in deformation at break were observed. TIFF0007864487000005.tif82170

[0126] Table 3 shows that for the block copolymers of the present invention (Ex3, Ex5, Ex7, Ex8 of the present invention), in which the flexible blocks are mainly PCL-based and positioned in contact with sebum, an increase in the elongation at break εR (%) is also observed.

[0127] The effect of improving the break point elongation of these TPE materials when the material is in contact with sebum, when mixed with at least 50% PCL, is a completely unexpected advantage observed in the copolymer of the present invention.

Claims

1. The use of polycaprolactone (PCL) to enhance the sebum resistance of a block copolymer in the preparation of a block copolymer comprising at least one rigid block and at least one flexible block, The rigid copolymer block is based on polyamide (PA), PCL accounts for at least 10% by weight of the flexible block relative to the total weight of the flexible block, which accounts for 100% of the total weight of the flexible block. use.

2. The use according to claim 1, wherein the rigid block is based on PA comprising at least one of the following polyamides: PA12, PA11, PA1010, PA6, PA6 / 12 and / or the following polyamide monomers: 11, 54, 59, 510, 512, 513, 514, 516, 518, 536, 64, 69, 610, 612, 613, 614, 616, 618, 636, 104, 109, 1010, 1012, 1013, 1014, 1016, 1018, 1036, 10T, 124, 129, 1210, 1212, 1213, 1214, 1216, 1218, 1236, 12T and mixtures thereof or copolyamides thereof.

3. The use according to claim 1 or 2, characterized in that the flexible block (BS) comprises, in addition to PCL, at least one polymer selected from polyethers; polyesters; polysiloxanes; polyolefins; polycarbonates; and mixtures thereof.

4. The use according to claim 1 or 2, wherein the PCL constitutes 100% of the flexible block.

5. The use of PCL in a copolymer having a rigid block and a flexible block according to any one of claims 1 to 3, wherein PCL accounts for 50 to 100% by weight of the flexible block relative to the total weight of the flexible block which accounts for 100%, in order to enhance the sebum resistance of the block copolymer without impairing its tensile mechanical properties.

6. The use of PCL in a copolymer having a rigid block and a flexible block according to any one of claims 1 to 3 and 5, wherein PCL constitutes 50 to 100% by weight of the flexible block relative to the total weight of the flexible block which accounts for 100%, in order to enhance the sebum resistance of the block copolymer and to enhance the elongation at the break point of the copolymer when the copolymer comes into contact with sebum.

7. Rigid block, and Flexible block containing at least 50% by weight of polycaprolactone (PCL) relative to the total weight of the flexible block, which accounts for 100% of the total weight. A sebum-resistant block copolymer characterized by containing, The rigid copolymer block is based on polyamide (PA), Polycaprolactone (PCL) has a number-average molar mass Mn in the range of 400 to 10,000 g / mol. Copolymer.

8. The copolymer according to claim 7, wherein the rigid block is PA-based and comprises at least one of the following polyamides: PA12, PA11, PA1010, PA6, PA6 / 12, and / or the following polyamide monomers: 11, 54, 59, 510, 512, 513, 514, 516, 518, 536, 64, 69, 610, 612, 613, 614, 616, 618, 636, 104, 109, 1010, 1012, 1013, 1014, 1016, 1018, 1036, 10T, 124, 129, 1210, 1212, 1213, 1214, 1216, 1218, 1236, 12T, and mixtures thereof or copolyamides thereof.

9. The copolymer according to claim 7 or 8, wherein the flexible block (FB) comprises, in addition to PCL, at least one of the following polymers: polyether; polyester; polysiloxane; polyolefin; polycarbonate; and mixtures thereof.

10. A method for synthesizing a block copolymer according to any one of claims 7 to 9, comprising polycondensation of at least one rigid block and at least one flexible block containing more than 50% by weight of PCL relative to the total weight of the flexible block.

11. A sebum-resistant polymer composition characterized by comprising at least one copolymer according to any one of claims 7 to 9, diluted with a thermoplastic polymer matrix.

12. The composition according to claim 11, wherein the polymer matrix comprises at least one homopolymer or copolymer thermoplastic polymer selected from polyolefins, polyamides, fluoropolymers, saturated polyesters, polycarbonates, styrene resins, PMMAs, thermoplastic polyurethanes (TPUs), ethylene-vinyl acetate copolymers (EVA), copolymers having polyamide blocks and polyether blocks, copolymers having polyester blocks and polyether blocks, copolymers having polyamide blocks, polyether blocks and polyester blocks, copolymers of ethylene and alkyl (meth)acrylates, copolymers of ethylene and vinyl alcohol (EVOH), ABS, SAN, ASA, polyacetals, polyketones, and mixtures thereof.

13. The composition according to any one of claims 11 and 12, comprising 1 to 99% by weight of the copolymer and 1 to 99% by weight of the matrix polymer, based on the total weight of the composition accounting for 100%.

14. Articles obtained by injection molding, overmolding, extrusion, co-extrusion, hot compression molding or multi-shot injection molding from at least one copolymer according to any one of claims 7 to 9, or from a composition according to any one of claims 11 to 13.

15. An article obtained by 3D printing from a copolymer powder according to any one of claims 7 to 9, or from a composition powder according to any one of claims 11 to 13.

16. The item, - Footwear; - Sports goods; - Clothing, accessories, or personal protective equipment; - optical articles; - Articles for automobiles, railways, or aircraft; - Structural, padding, or damping articles; - Articles for childcare or toys, or for parts of strollers, prams, or baby carriers; - Medical supplies; - Electrical and / or electronic articles The article according to either claim 14 or 15.

17. The article according to any one of claims 14 to 16, wherein the article is an electrical or electronic article comprising a casing or protective casing manufactured from a copolymer according to any one of claims 7 to 9, or from a composition according to any one of claims 11 to 13.

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