Antistatic transparent polymer composition

Abstract

The present invention relates to copolymers having polyamide blocks and having polyether blocks containing aromatic units, and their use as antistatic additives.The present invention also relates to transparent antistatic compositions comprising at least one copolymer having polyamide blocks and having polyether blocks and a thermoplastic polymer matrix.

Description

[Technical field]

[0001] The present invention relates to copolymers having polyamide blocks and having polyether blocks containing aromatic units, and their use as antistatic additives.The present invention also relates to a transparent antistatic composition comprising at least one copolymer having polyamide blocks and polyether blocks and a thermoplastic polymer matrix. [Background technology]

[0002] It is known that static electricity is generated and retained on the surfaces of most plastics. For example, the presence of static electricity on thermoplastic films can cause these films to stick to each other and make separation difficult. The presence of static electricity on packaging films can cause dust to adhere to the packaged object and hinder its use. Static electricity can also damage components of microprocessors and electronic circuits. Furthermore, static electricity can cause the combustion and explosion of flammable materials, for example expandable polystyrene beads containing pentane.

[0003] Antistatic agents for polymers have been described in the prior art. They are generally ionic surfactants of the sulfonate or ethoxylated amine type that are added to the polymer. However, the antistatic properties of polymers incorporating these surfactants are not permanent, since they depend on the humidity of the surroundings. This is because these surfactants tend to migrate to the surface of the polymer and then disappear.

[0004] Hydrophilic copolymers with polyamide and polyether blocks constitute another category of antistatic agents and present the advantage of not migrating. Their antistatic properties are permanent and unaffected by ambient humidity. In particular, patents JP 60023435 A, EP 242 158, WO 0110951, EP 1 046 675 and EP 829 520 are mentioned, which describe polymer substrates that are rendered antistatic by adding to the composition copolymers with polyether and polyamide blocks.

[0005] Additionally, there is currently a need to impart antistatic properties to transparent polymers. However, it has been found that the addition of antistatic agents to a transparent polymer matrix compromises the transparency of the combination. This is because, as will be explained in more detail below, the antistatic additives tend to be located at the surface of the material. While this location is beneficial for the antistatic properties imparted to the material, it has the disadvantage of affecting the transparency of the material.

[0006] In particular, it has been observed that when sulfonate salts, known as antistatic additives, are added to a transparent polymer matrix, the antistatic properties are not permanent: the salts tend to migrate to the surface and are gradually removed after repeated rubbing or cleaning operations of this surface.

[0007] Block polymers have also been used as antistatic additives in transparent matrices.

[0008] US 2006 / 0281860 A relates to a thermoplastic resin for producing a molded article having satisfactory transparency, good permanent antistatic properties and good mechanical properties. The transparent resin composition in this document contains at least a block polymer and a transparent resin, and the difference in refractive index between the block polymer and the transparent resin is 0.01 or less. The block copolymer has a refractive index of 1.575 or more and a refractive index of 10 12 ~10 17 An aromatic ring-containing oleophilic block having a volume resistivity of 10 5~10 11 It is composed of a hydrophilic block containing an aromatic ring, which has a volume resistivity of Ω·cm and a thermal decomposition temperature of 250 to 380°C.

[0009] The document JP 2016166332 relates to an antistatic agent that imparts excellent transparency to a molded article and also imparts permanent antistatic properties and mechanical properties. The antistatic agent contains a block polymer and has a refractive index of 1500 to 1600, and the block polymer contains at least one hydrophobic polymer block selected from the group consisting of polyamide, polyolefin, and polyamideimide, a hydrophilic polymer block, and a hydrophobic polyether block containing an aromatic ring as a constituent unit.

[0010] However, these proposed solutions are not satisfactory.

[0011] Therefore, there is a real need to provide a transparent composition that has durable antistatic properties without affecting the mechanical properties of the composition. Summary of the Invention

[0012] The present invention relates first to a block copolymer comprising at least one polyamide block and at least one polyether block (PEBA), said block copolymer comprising: the polyamide block comprises at least one unit of formula XDY, in which XD represents units derived from m-xylylenediamine (MXD), p-xylylenediamine (PXD) and mixtures thereof, preferably m-xylylenediamine; Y represents a unit derived from a linear or branched aliphatic, alicyclic or aromatic dicarboxylic acid containing 4 to 36 carbon atoms; the polyether blocks contain ethylene oxide units in a content of at least 20% relative to the total weight of the copolymer, The content of aromatic units is between 20% and 80% by weight of the total copolymer. It is characterized by:

[0013] Preferably, the copolymer exhibits a refractive index of 1.51 or greater.

[0014] According to a particular embodiment, the dicarboxylic acid (Y) is selected from aliphatic diacids having from 6 to 36 carbon atoms, preferably from 6 to 18 carbon atoms, more preferably from 9 to 18 carbon atoms, in particular 1,10-decanedicarboxylic acid (represented by 10), 1,11-undecanedicarboxylic acid (represented by 11), 1,12-dodecanedicarboxylic acid (represented by 12), 1,14-tetradecanedicarboxylic acid (represented by 14) and 1,18-octadecanedicarboxylic acid (represented by 18), and aromatic dicarboxylic acids having from 6 to 36 carbon atoms, in particular terephthalic acid (represented by T), isophthalic acid (represented by I), naphthalenedicarboxylic acid (represented by N) and 2,5-furandicarboxylic acid.

[0015] According to a particular embodiment, the polyamide block comprises at least one additional unit of formula Z, where Z represents an amino acid unit, a lactam unit or a unit resulting from polycondensation of a unit corresponding to formula (Ca diamine)·(Cb dicarboxylic acid), where Ca and Cb each can contain from 4 to 36 carbon atoms.

[0016] According to a particular embodiment, the polyamide blocks are selected from XDI, XDT, XD10 / XDI, XD10 / XDT, 11 / XDI, 11 / XDT, XD10 / XDI / XDT or 11 / XDI / XDT.

[0017] According to a particular embodiment, the ethylene oxide units are derived from polyethylene glycol or polyetheramines comprising ethylene oxide units.

[0018] The present invention also provides (a) at least one block copolymer comprising at least one polyamide block and at least one polyether block, the polyamide block comprising at least one unit of formula AY, wherein: -A represents a unit derived from a linear or branched aliphatic, alicyclic or alkyl aromatic diamine containing 4 to 36 carbon atoms; -Y represents a unit derived from a dicarboxylic acid as defined above, the content of polyether blocks of ethylene oxide units is greater than or equal to 30% relative to the total weight of the copolymer, at least one block copolymer, the content of aromatic units being between 20% and 80% relative to the total weight of the copolymer; (b) a transparent thermoplastic polymer matrix comprising at least one thermoplastic polymer exhibiting a refractive index of 1.51 or greater; The present invention relates to a transparent antistatic polymer composition comprising:

[0019] Preferably, the block copolymer present in the composition exhibits a refractive index of 1.51 or greater.

[0020] According to a particular embodiment, the diamine (A) is selected from the group consisting of butanediamine (represented by 4), pentanediamine (represented by 5), hexanediamine (represented by 6), heptanediamine (represented by 7), octanediamine (represented by 8), nonanediamine (represented by 9), decanediamine (represented by 10), undecanediamine (represented by 11), dodecanediamine (represented by 12), tridecanediamine (represented by 13), tetradecanediamine (represented by 14), hexadecanediamine (represented by 16), octadecanediamine (represented by 17), octadecanediamine (represented by 18), octadecanediamine (represented by 19), octadecanediamine (represented by 20), octadecanediamine (represented by 21), octadecanediamine (represented by 22), octadecanediamine (represented by 23), octadecanediamine (represented by 24), octadecanediamine (represented by 25), octadecanediamine (represented by 26), octadecanediamine (represented by 27), octadecanediamine (represented by 28), octadecanediamine (represented by 29), octadecanediamine (represented by 30), octadecanediamine (represented by 31), octadecanediamine (represented by 32), octadecanediamine (represented by 33), octadecanediamine (represented by 34), octadecanediamine (represented by 35), octadecanediamine (represented by 36), octadecanediamine (re The diamines are selected from diamines derived from fatty acids, bis(3-methyl-4-aminocyclohexyl)methane (represented by BMACM or MACM), isopropylidenedi(cyclohexylamine) (represented by PACP), m-xylylenediamine (MXD), p-xylylenediamine (PXD) and mixtures thereof, and preferably m-xylylenediamine.

[0021] According to a particular embodiment, the ethylene oxide units are derived from polyethylene glycol or polyetheramines comprising ethylene oxide units.

[0022] According to a particular embodiment, the thermoplastic polymer of the matrix is ​​selected from polycarbonate (PC), polystyrene, polyethylene terephthalate (PET), polyethylene terephthalate glycol (PETG), polysulfone, acrylonitrile-butadiene-styrene (ABS), styrene-acrylonitrile (SAN), acrylonitrile-styrene-acrylate (ASA), copolymers thereof and alloys thereof.

[0023] According to one embodiment, the polyamide block further comprises at least one unit resulting from polycondensation of an amino acid or a lactam unit.

[0024] According to a particular embodiment, the polyamide blocks of the copolymer are chosen from 6I / 6T, 410 / 4T, 11 / 10T, 11T, 5I / 5T, XDI, 11 / XDI, XDT, XD10 / XDI, XD10 / XDT, 11 / XDT, XD10 / XDI / XDT or 11 / XDI / XDT, and / or the thermoplastic polymer matrix is ​​chosen from PC, PET or PETG, and / or the content of aromatic units is between 35% and 60% relative to the total weight of the copolymer.

[0025] According to certain embodiments, the composition further comprises an organic salt.

[0026] The present invention also relates to the use of said copolymers as antistatic additives.

[0027] The present invention makes it possible to meet the above-mentioned needs by providing a transparent composition, more particularly a transparent polymeric composition, which has permanent antistatic properties without affecting the mechanical properties of the composition.

[0028] This is achieved by incorporating specific copolymers into a transparent thermoplastic polymer matrix. More specifically, the presence of a copolymer having polyamide blocks and having polyether blocks with a weight content of ethylene oxide units (as polyether blocks) of 20% or more relative to the weight of the copolymer, on the one hand, and the presence in the copolymer of 20% to 80% by weight of aromatic groups relative to the weight of the copolymer, on the other hand, makes it possible to obtain a high refractive index as well as to improve the antistatic properties of the composition. This refractive index is 1.51 or more, which is close to the refractive index of the matrix used, so that the composition can be formed without affecting the transparency of the matrix.

[0029] Detailed Description The invention will now be explained in more detail in the following non-limiting manner.

[0030] The nomenclature used to define polyamides is described in standard ISO 1874-1:1992 "Plastics - Polyamide (PA) moulding and extrusion materials - Part 1: Designation", in particular page 3 (Tables 1 and 2) and is well known to the person skilled in the art.

[0031] The term "copolymer" is understood to mean a polymer resulting from the copolymerization of at least two chemically different monomers, called comonomers. Thus, a copolymer is formed from at least two different repeat units. It can also be formed from three or more repeat units. More particularly, the term "block copolymer" is understood to refer to a copolymer in the above sense, in which at least two different monomer blocks are linked by covalent bonds. The length of the blocks is variable. Preferably, the blocks are each composed of 1 to 1000, preferably 1 to 100, in particular 1 to 50 repeat units. The bond between two monomer blocks may require an intermediate non-repeating unit, known as a junction block.

[0032] Block copolymers containing at least one polyamide block and at least one polyether block (PEBA) PEBA copolymers result from the polycondensation of polyamide blocks having reactive ends and polyether blocks having reactive ends, among others: 1) a polyamide block having diamine chain ends and a polyoxyalkylene block having di(carboxylic acid) chain ends; 2) polyamide blocks with di(carboxylic acid) chain ends carrying polyoxyalkylene blocks with diamine chain ends, for example obtained by cyanoethylation and hydrogenation of α,ω-dihydroxylated aliphatic polyoxyalkylene blocks known as polyether diols, or alternatively 3) A polyamide block having di(carboxylic acid) chain ends with a polyether diol; in this particular case the resulting product is a polyetheresteramide.

[0033] Polyamide blocks with di(carboxylic acid) chain ends result, for example, from the condensation of polyamide precursors in the presence of a dicarboxylic acid chain limiter. Polyamide blocks with diamine chain ends result, for example, from the condensation of polyamide precursors in the presence of a diamine chain limiter.

[0034] The polymers having polyamide and polyether blocks can also contain randomly distributed units.

[0035] Polyamide Block In the unit of formula XDY according to the invention: XD represents units derived from m-xylylenediamine, p-xylylenediamine and mixtures thereof, preferably m-xylylenediamine; Y represents a unit derived from a dicarboxylic acid containing from 4 to 36 carbon atoms, preferably from 6 to 14 carbon atoms, more particularly from isophthalic acid or terephthalic acid.

[0036] The dicarboxylic acids (Y) may be linear or branched, aliphatic, alicyclic or aromatic.

[0037] The aliphatic diacid may be selected from succinic acid (n=4), pentanedioic acid (n=5), adipic acid (n=6), heptanedioic acid (n=7), octanedioic acid (n=8), azelaic acid (n=9), sebacic acid (n=10), undecanedioic acid (n=11), dodecanedioic acid (n=12), brassylic acid (n=13), tetradecanedioic acid (n=14), hexadecanedioic acid (n=16), octadecanedioic acid (n=18), octadecanedioic acid (n=18), eicosanediocic acid (n=20), docosanediocic acid (n=22), and fatty acid dimers. The abovementioned fatty acid dimers are in particular dimerized fatty acids obtained by oligomerization or polymerization of unsaturated monobasic fatty acids with long hydrocarbon chains, such as linoleic acid and oleic acid, as described in EP 0 471 566.

[0038] The alicyclic diacids can include the following carbon backbones: norbornylmethane, cyclohexylmethane, dicyclohexylmethane, dicyclohexylpropane, di(methylcyclohexyl) or di(methylcyclohexyl)propane.

[0039] The aromatic diacids may be selected from terephthalic acid (represented by T), isophthalic acid (represented by I) and naphthalenedioic acid (represented by N), 2,5-furandicarboxylic acid, and naphthalenedioic acid.

[0040] Advantageously, the XDY units are selected from MXD10, MXD11, PXD10, PXD11, MXDT, MXDI, PXDT and PXDI.

[0041] The additional units Z according to the invention refer to amino acid units, lactam units or units obtained by polycondensation of units corresponding to the formula (Ca diamine)·(Cb diacid). The polyamide block can therefore be of the formula XDY / Z.

[0042] The amino acid units may be selected from 9-aminononanoic acid, 10-aminodecanoic acid, 10-aminoundecanoic acid, 12-aminododecanoic acid and 11-aminoundecanoic acid, and derivatives thereof, in particular N-heptyl-11-aminoundecanoic acid.

[0043] The lactam unit may be selected from pyrrolidinone, 2-piperidinone, enantholactam, caprylolactam, pelargolactam, decanolactam, undecanolactam and lauryllactam.

[0044] With respect to the units corresponding to the formula (Ca diamine)·(Cb diacid), the (Ca diamine) units may be selected from linear or branched aliphatic or cycloaliphatic diamines and the (Cb diacid) units may be selected from linear or branched aliphatic, cycloaliphatic or aromatic diacids, as defined above for the Y units.

[0045] Linear and aliphatic diamines are typically represented by the formula H2N-(CH2) m It is represented by -NH2 and can be selected from butanediamine (m=4), pentanediamine (m=5), hexanediamine (m=6), heptanediamine (m=7), octanediamine (m=8), nonanediamine (m=9), decanediamine (m=10), undecanediamine (m=11), dodecanediamine (m=12), tridecanediamine (m=13), tetradecanediamine (m=14), hexadecanediamine (m=16), octadecanediamine (m=18), octadecenediamine (m=18), eicosanediamine (m=20), docosanediamine (m=22) and diamines obtained from fatty acids.

[0046] When the diamine is aliphatic and branched, it may contain one or more methyl or ethyl substituents on the backbone and may be selected, for example, from 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 1,3-diaminopentane, 2-methyl-1,5-pentanediamine, or 2-methyl-1,8-octanediamine.

[0047] The alicyclic diamine may be selected from bis(3,5-dialkyl-4-aminocyclohexyl)methane, bis(3,5-dialkyl-4-aminocyclohexyl)ethane, bis(3,5-dialkyl-4-aminocyclohexyl)propane, bis(3,5-dialkyl-4-aminocyclohexyl)butane, bis(3-methyl-4-aminocyclohexyl)methane (BMACM or MACM), bis(p-aminocyclohexyl)methane (PACM) and isopropylidenedi(cyclohexylamine) (PACP). It may also contain the following carbon skeletons: norbornylmethane, cyclohexylmethane, dicyclohexylpropane, di(methylcyclohexyl) or di(methylcyclohexyl)propane. A non-exhaustive list of these cycloaliphatic diamines can be found in the publication "Cycloaliphatic Amines" (Encyclopedia of Chemical Technology, Kirk-Othmer, 4th Edition (1992), pages 386-405).

[0048] Advantageously, the PA block of formula XDY / Z is selected from the XD10 / XD11, 11 / XDI, XD10 / XDI / XDT, 11 / XDI / XDT, XD10 / XDI / XDN or 11 / XDI / XDN blocks.

[0049] The PEBA copolymer may contain polyamide blocks in a content of 35% by weight or more relative to the total weight of the copolymer.

[0050] Preferably, the number average molar mass Mn of the PA block is between 400 and 20 000 g / mol, preferably between 500 and 10 000 g / mol.

[0051] Polyether Block The polyether blocks are composed of alkylene oxide units, which can usually be ethylene oxide units, propylene oxide units, or tetrahydrofuran units (leading to polytetramethylene glycol sequences).

[0052] The copolymer according to the invention comprises ethylene oxide units (PEG).

[0053] The copolymer may optionally contain propylene oxide units (PPG), polytrimethylene oxide units (PO3G) and / or tetramethylene oxide units (PTMG) and is also called polytetrahydrofuran. PEBA copolymers may contain several types of polyethers in their chains, and the copolyethers may be in block or random form.

[0054] The polyether blocks can be polyether diol blocks, which are used as such and copolycondensed with polyamide blocks having carboxyl end groups, or aminated to convert them to polyether diamines and then condensed with polyamide blocks having carboxyl end groups.

[0055] The PEBA copolymer according to the invention comprises ethylene oxide units in a content of at least 20%, preferably at least 25%, preferably at least 30%, preferably at least 40% and more preferably at least 50% by weight relative to the total weight of the copolymer. Preferably, the PEBA copolymer according to the invention comprises ethylene oxide units in a content between 20% and 80% by weight, more preferably between 25% and 55% by weight relative to the total weight of the copolymer.

[0056] According to certain embodiments, the copolymer of the composition further comprises at least one polyether other than PEG selected from PTMG, PPG, PO3G and blends thereof.

[0057] It is also possible to use blocks obtained by oxyethylation of bisphenols, such as, for example, bisphenol A. The latter products are described in patent EP 613 919.

[0058] Preferably, the copolymer according to the invention does not comprise polyether blocks derived from ethoxylated bisphenols, since it has been found that the absence of this polyether unit enhances the mechanical properties imparted by the copolymer.

[0059] The polyether blocks may also consist of ethoxylated primary amines. Examples of ethoxylated primary amines include products of the formula: TIFF2024528071000001.tif25170, where m and n are between 1 and 20, and x is between 8 and 18. These products are commercially available from Arkema under the Noramox® brand and from Clariant under the Genamin® brand.

[0060] The polyether block can comprise a polyoxyalkylene block with NH2 chain end, such a block can be obtained by cyanoacetylation of α,ω-dihydroxylated aliphatic polyoxyalkylene blocks known as polyether diols. More specifically, Jeffamine products can be used (e.g. Jeffamine® D400, D2000, ED2003, XTJ542, commercial products from Huntsman, also described in patent documents JP2004346274, JP2004352794 and EP1482011).

[0061] Preferably, the ethylene oxide units can be derived from a polyethylene glycol or from a polyetheramine containing ethylene oxide units.

[0062] The general methods for the two-step preparation of PEBA copolymers having ester bonds between the PA and PE blocks are known and are described, for example, in French patent FR 2 846 332. The general methods for preparing the inventive PEBA copolymers having amide bonds between the PA and PE blocks are known and are described, for example, in European patent EP 1 482 011. To prepare polymers having polyamide blocks and polyether blocks with randomly distributed units, the polyether blocks can also be mixed with the polyamide precursor and the diacid chain limiter (single-step process).

[0063] Of course, the designation PEBA in the description of this invention equally relates to Pebax® products sold by Arkema, to Vestamid® products sold by Evonik®, to Grilamid® products sold by EMS, to Pelestat® type PEBA products sold by Sanyo, or to other PEBA products from other suppliers.

[0064] Advantageously, the PEBA copolymer has PA blocks consisting of MXD10, MXD11, PXD10, PXD11, MXDT, MXDI, PXDT and PXDI, and polyetherdiol or polyetheramine blocks containing ethylene oxide units.

[0065] More preferably, the copolymer according to the invention is selected from: PA MXD10-PEG, PA MXD11-PEG, PA XD10-PEG, PA PXD11-PEG, PA MXDT-PEG, PA MXDI-PEG, PA PXDT-PEG, PA PXDI-PEG and / or mixtures thereof.

[0066] Aromatic Unit The PEBA copolymer according to the invention contains from 20% to 80% by weight, preferably from 20% to 60% by weight, preferably from 25% to 55% by weight of aromatic units relative to the total weight of the copolymer.

[0067] The term "aromatic unit" is understood in the context of the present invention to mean each unit that contains an aromatic group derived from a monomer. This unit may be present in the PA block and / or in the PE block of the PEBA copolymer, for example in the XD unit and, if necessary, in the terephthalic or isophthalic acid units, if present, or in the ethoxylated bisphenols. Thus, any unit that contains an aromatic group is taken into account in the calculation of this weight content.

[0068] According to one embodiment, the block copolymer according to the invention consists of at least one polyamide block and at least one polyether block, the polyamide block comprises at least one unit of formula XDY, in which XD represents units derived from m-xylylenediamine, p-xylylenediamine and mixtures thereof, preferably m-xylylenediamine; Y represents a unit derived from a linear or branched aliphatic, alicyclic or aromatic dicarboxylic acid containing 4 to 36 carbon atoms; the polyether blocks contain ethylene oxide units in a content of at least 20% relative to the total weight of the copolymer, at least one block copolymer, the content of aromatic units being between 20% and 80% relative to the total weight of the copolymer; -The copolymer has a refractive index of 1.51 or higher. It is characterized by:

[0069] According to a particular embodiment, the copolymer according to the invention is a block copolymer comprising three different types of blocks (called "triblock" in the present description) resulting from the condensation of several blocks. Said triblock may be a copolyetheresteramide or a copolyetheramideurethane, and comprises, relative to the total weight of the triblock, - the weight percentage of polyamide blocks is greater than 10%, The weight percentage of the PEG blocks is greater than 50%.

[0070] The copolymer according to the invention exhibits a refractive index of 1.51 or more, preferably 1.52 or more, preferably 1.53 or more, more preferably 1.55 or more. For example, the refractive index can be 1.51 to 1.52, or 1.52 to 1.54, or 1.54 to 1.56, or 1.56 to 1.58, or 1.58 to 1.60, or 1.60 to 1.62, or 1.62 to 1.64, or 1.64 to 1.66, or 1.66 to 1.68, or 1.68 to 1.70. The refractive index can be measured by known methods using an Abbe refractometer according to the ISO 489-1999 standard.

[0071] The number average molar mass of the polyamide blocks in the PEBA copolymer may, for example, preferably have a value of 400 to 10 000 g / mol, more preferably 500 to 10 000 g / mol. In an embodiment, the number average molar mass of the polyamide blocks in the PEBA copolymer has a value of 400-500 g / mol, or 500-600 g / mol, or 600-1000 g / mol, or 1000-1500 g / mol, or 1500-2000 g / mol, or 2000-2500 g / mol, or 2500-3000 g / mol, or 3000-3500 g / mol, or 3500-4000 g / mol, or 4000-5000 g / mol, or 5000-6000 g / mol, or 6000-7000 g / mol, or 7000-8000 g / mol, or 8000-9000 g / mol, or 9000-10000 g / mol.

[0072] The number average molar mass of the polyether blocks may preferably have a value of 100 to 3000 g / mol, more preferably 200 to 3000 g / mol. In an embodiment, the number average molar mass of the polyether blocks has a value of 100 to 200 g / mol, or 200 to 500 g / mol, or 500 to 800 g / mol, or 800 to 1000 g / mol, or 1000 to 1500 g / mol, or 1500 to 2000 g / mol, or 2000 to 2500 g / mol, or 2500 to 3000 g / mol.

[0073] The number average molar mass can be determined by the chain limiter content and can be calculated according to the following equation: M n =n モノマー ×MW 繰り返し単位 / n チェーンリミッター +MW チェーンリミッター

[0074] In the formula, n モノマー represents the number of moles of monomer, and n チェーンリミッター represents the number of moles of excess diacid limiter, and MW 繰り返し単位 represents the molar mass of the repeating unit, and MW チェーンリミッター represents the molar mass of the excess diacid.

[0075] The Mn measurement protocol is described in the paper "Synthesis and characterization of poly(copolyethers-block-polyamides) - II. Characterization and properties of the multiblock copolymers", Marechal et al., Polymer, Volume 41, 2000, 3561-3580.

[0076] Advantageously, the weight ratio of the polyamide blocks to the polyether blocks of the copolymer has a value between 0.1 and 20, preferably between 0.5 and 18, more preferably between 0.6 and 15. This weight ratio can be calculated by dividing the number-average molar mass of the polyamide blocks by the number-average molar mass of the polyether blocks. In particular, the weight ratio of the polyamide blocks to the polyether blocks of the copolymer is between 0.1 and 0.2, or between 0.2 and 0.3, or between 0.3 and 0.4, or between 0.4 and 0.5, or between 0.5 and 0.6, or between 0.6 and 0.7, or between 0.7 and 0.8, or between 0.8 and 0.9, or between 0.9 and 1, or between 1 and 1.5, or between 1.5 and 2, or between 2 and 2.5, or between 2.5 and 3, or between 3 and 3.5, or between 3.5 and 4, or between 4 and 4.5. , or 4.5 to 5, or 5 to 5.5, or 5.5 to 6, or 6 to 6.5, or 6.5 to 7, or 7 to 7.5, or 7.5 to 8, or 8 to 8.5, or 8.5 to 9, or 9 to 9.5, or 9.5 to 10, or 10 to 11, or 11 to 12, or 12 to 13, or 13 to 14, or 14 to 15, or 15 to 16, or 16 to 17, or 17 to 18, or 18 to 19, or 19 to 20.

[0077] Advantageously, the PEBA copolymer has a Shore D hardness greater than or equal to 30. The hardness measurement can be carried out according to standard ISO 7619-1.

[0078] Advantageously, the copolymer exhibits an intrinsic viscosity between 0.6 and 2, preferably between 0.6 and 1.5, and preferably between 0.8 and 1.4.

[0079] As used herein, inherent viscosity is measured using an Ubbelohde viscometer at 20° C. in a meta-cresol solution with a polymer concentration of 0.5% by weight based on the total weight of the solution.

[0080] The PEBA copolymers described above can be used as antistatic additives in compositions (eg, compositions that include a thermoplastic polymer matrix) to improve the antistatic properties of the composition.

[0081] Antistatic transparent polymer composition The term "transparent composition" is understood to mean a composition that exhibits a transmittance at least equal to 88% according to standard ASTM D1003-97 / ISO 13468, and a haze of less than 15%, preferably less than 10%, preferably less than 5%, according to the ASTM D1003-97 standard, these two properties being measured at 560 nm on a plate with a thickness of 2 mm.

[0082] The term "antistatic composition" refers to a composition having a surface resistivity (or surface resistivity) of 10 12 is understood to mean a composition which is less than Ω / square.

[0083] The polyamide block of copolymer (a) comprises at least one unit of formula AY, In the formula, A represents a unit derived from a linear or branched aliphatic, alicyclic or alkyl aromatic diamine, Y represents a unit derived from a dicarboxylic acid as defined above.

[0084] The linear or branched aliphatic and cycloaliphatic diamines are as defined above for the Ca diamines.

[0085] The alkylaromatic diamine may be selected from m-xylylenediamine and p-xylylenediamine.

[0086] According to one embodiment, the unit A is butanediamine (represented by 4), pentanediamine (represented by 5), hexanediamine (represented by 6), heptanediamine (represented by 7), octanediamine (represented by 8), nonanediamine (represented by 9), decanediamine (represented by 10), undecanediamine (represented by 11), dodecanediamine (represented by 12), tridecanediamine (represented by 13), tetradecanediamine (represented by 14), hexadecanediamine (represented by 16), octadecanediamine (represented by 17), octadecanediamine (represented by 18), octadecanediamine (represented by 19), octadecanediamine (represented by 20), octadecanediamine (represented by 21), octadecanediamine (represented by 22), octadecanediamine (represented by 23), octadecanediamine (represented by 24), octadecanediamine (represented by 25), octadecanediamine (represented by 26), octadecanediamine (represented by 27), octadecanediamine (represented by 28), octadecanediamine (represented by 29), octadecanediamine (represented by 30), octadecanediamine (represented by 31), octadecanediamine (represented by 32), octadecanediamine (represented by 33), octadecanediamine (represented by 34), octadecanediamine (represented by 35), octadecanediamine (represented by 36), octadecanediamine (represented by 37), octa The diamines are selected from diamines derived from fatty acids, bis(3-methyl-4-aminocyclohexyl)methane (designated BMACM or MACM), isopropylidenedi(cyclohexylamine) (designated PACP), m-xylylenediamine, p-xylylenediamine and mixtures thereof, and preferably m-xylylenediamine.

[0087] The diacid Y is as defined above.

[0088] The polyether blocks are as defined above.

[0089] According to one embodiment, the polyamide blocks contained in the composition further comprise at least one unit resulting from the polycondensation of an amino acid or lactam unit, as described above.

[0090] Preferably, the polyamide blocks of the copolymers present in the composition according to the invention are selected from 6I / 6T, 410 / 4T, 11 / 10T, 11T, 5I / 5T, XDI, 11 / XDI, XDT, XD10 / DXI, XD10 / DXT, 11 / XDT, XD10 / XDI / XDT, 11 / XDI / XDT, XD10 / XDI / XDN or 11 / XDI / XDN.

[0091] According to a particular embodiment, the copolymer comprised in the composition according to the invention may be a triblock, the third block being as defined above.

[0092] The number average molar mass of the polyamide blocks in the PEBA copolymer preferably has a value of 400 to 10 000 g / mol, more preferably 500 to 6000 g / mol. In an embodiment, the number average molar mass of the polyamide blocks in the PEBA copolymer has a value of 400-500 g / mol, or 500-600 g / mol, or 600-1000 g / mol, or 1000-1500 g / mol, or 1500-2000 g / mol, or 2000-2500 g / mol, or 2500-3000 g / mol, or 3000-3500 g / mol, or 3500-4000 g / mol, or 4000-5000 g / mol, or 5000-6000 g / mol, or 6000-7000 g / mol, or 7000-8000 g / mol, or 8000-9000 g / mol, or 9000-10000 g / mol.

[0093] The number average molar mass of the polyether blocks preferably has a value between 100 and 3000 g / mol, more preferably between 200 and 2000 g / mol. In an embodiment, the number average molar mass of the polyether blocks has a value between 100 and 200 g / mol, or between 200 and 500 g / mol, or between 500 and 800 g / mol, or between 800 and 1000 g / mol, or between 1000 and 1500 g / mol, or between 1500 and 2000 g / mol, or between 2000 and 2500 g / mol, or between 2500 and 3000 g / mol.

[0094] Advantageously, the weight ratio of the polyamide blocks to the polyether blocks of the copolymer has a value between 0.1 and 20, preferably between 0.5 and 18, more preferably between 0.6 and 15. This weight ratio can be calculated by dividing the number-average molar mass of the polyamide blocks by the number-average molar mass of the polyether blocks. In particular, the weight ratio of the polyamide blocks to the polyether blocks of the copolymer is between 0.1 and 0.2, or between 0.2 and 0.3, or between 0.3 and 0.4, or between 0.4 and 0.5, or between 0.5 and 0.6, or between 0.6 and 0.7, or between 0.7 and 0.8, or between 0.8 and 0.9, or between 0.9 and 1, or between 1 and 1.5, or between 1.5 and 2, or between 2 and 2.5, or between 2.5 and 3, or between 3 and 3.5, or between 3.5 and 4, or between 4 and 4.5. , or 4.5 to 5, or 5 to 5.5, or 5.5 to 6, or 6 to 6.5, or 6.5 to 7, or 7 to 7.5, or 7.5 to 8, or 8 to 8.5, or 8.5 to 9, or 9 to 9.5, or 9.5 to 10, or 10 to 11, or 11 to 12, or 12 to 13, or 13 to 14, or 14 to 15, or 15 to 16, or 16 to 17, or 17 to 18, or 18 to 19, or 19 to 20.

[0095] Advantageously, the copolymers having polyamide blocks and polyether blocks have a Shore D hardness greater than or equal to 30. The hardness measurement can be carried out according to standard ISO 7619-1.

[0096] The copolymers contained in the composition according to the invention exhibit a refractive index of 1.51 or more, preferably 1.52 or more, preferably 1.53 or more, more preferably 1.55 or more. For example, the refractive index can be 1.51 to 1.52, or 1.52 to 1.54, or 1.54 to 1.56, or 1.56 to 1.58, or 1.58 to 1.60, or 1.60 to 1.62, or 1.62 to 1.64, or 1.64 to 1.66, or 1.66 to 1.68, or 1.68 to 1.70. The refractive index can be measured by known methods using an Abbe refractometer according to the ISO 489-1999 standard.

[0097] Advantageously, the copolymer exhibits an intrinsic viscosity between 0.6 and 2, preferably between 0.6 and 1.5, and preferably between 0.8 and 1.4.

[0098] The composition according to the invention may have a weight content of PEBA copolymer of from 0.1% to 45%, and preferably from 3% to 35%, preferably from 5% to 30%, and even more preferably from 5% to 20%, relative to the weight of the composition.

[0099] The composition according to the present invention also includes a transparent thermoplastic polymer matrix that exhibits a refractive index of 1.51 or greater.

[0100] Preferably, the difference in refractive index between the copolymer and the transparent thermoplastic polymer matrix is ​​less than 0.02.

[0101] The thermoplastic matrix comprises at least one thermoplastic polymer, which is a homopolymer or copolymer selected from polyolefins, polyamides, fluoropolymers, saturated polyesters, polycarbonates (PC), styrene resins, polysulfones, copolymers with polyamide blocks, copolymers with polyether blocks, and copolymers with polyester blocks, copolymers of ethylene and alkyl (meth)acrylates, copolymers of ethylene and vinyl alcohol (EVOH), acrylonitrile-butadiene-styrene (ABS), polysulfones, styrene-acrylonitrile (SAN), acrylonitrile-styrene-acrylate (ASA), polyacetals, polyketones, copolymers thereof, and alloys thereof.

[0102] According to a preferred embodiment, the thermoplastic matrix is ​​selected from polycarbonate, polystyrene, polyethylene terephthalate, polyethylene terephthalate glycol, polysulfone, acrylonitrile-butadiene-styrene (ABS), styrene-acrylonitrile (SAN), acrylonitrile-styrene-acrylate (ASA), copolymers thereof and alloys thereof.

[0103] More particularly, the matrix of the composition according to the invention is chosen from polycarbonates, polyterephthalates and polyethylene terephthalate glycols.

[0104] The term "matrix" is understood within the meaning of the present invention to mean a material present in a content of more than 50% by weight of the composition.

[0105] According to one embodiment of the composition according to the invention, the polyamide blocks of the copolymer are selected from 6I / 6T, 410 / 4T, 11 / 10T, 11T, 5I / 5T, XDI, 11 / XDI, XDT, XD10 / XDI, XD10 / XDT, 11 / XDT, XD10 / XDI / XDT or 11 / XDI / XDT, the thermoplastic polymer matrix is ​​selected from PC, PET or PETG, and the content of aromatic units is between 35% and 60% relative to the total weight of the copolymer.

[0106] The composition according to the invention may have a weight content of thermoplastic matrix of 55% to 99.9%, preferably 65% ​​to 97%, preferably 70% to 95%, more preferably 80% to 93%, relative to the weight of the composition.

[0107] Advantageously, the compositions of the present invention, due to their permanent antistatic properties, have a surface (or superficial) resistivity of 10 12 Since it is less than Ω / square, it does not require organic salts and therefore does not contain organic salts.

[0108] Nevertheless, it is possible to incorporate organic salts into the composition according to the invention in order to further improve its antistatic performance qualities.

[0109] Advantageously, the composition according to the invention further comprises between 0.1% and 10% by weight, preferably between 0.1% and 5% by weight, of at least one organic salt in the molten state relative to the total weight of the composition.

[0110] An organic salt is a salt in which an organic cation is combined with an inorganic or organic anion.

[0111] The at least one organic salt is added in the molten state, i.e. when the organic salt is at a temperature above its melting point. Preferably, the at least one organic salt has a melting point below 300° C., preferably below 200° C., preferably below 100° C., and advantageously constitutes an ionic liquid, preferably below 30° C. In particular, ionic liquids are non-volatile (no volatile organic compounds diffuse into the atmosphere), non-flammable (hence easy to handle and store), stable at high temperatures (up to 400° C. in some cases), very good conductors and very stable to water and oxygen.

[0112] Advantageously, said at least one organic salt comprises at least one cation comprising at least one of the following molecules: ammonium, sulfonium, pyridinium, pyrrolidinium, imidazolium, imidazolinium, phosphonium, lithium, guanidinium, piperidinium, thiazolium, triazolium, oxazolium, pyrazolium and mixtures thereof.

[0113] Advantageously, said at least one organic salt comprises at least one anion comprising at least one of the following molecules: imides, in particular bis(trifluoromethanesulfonyl)imide (abbreviated NTf2-); borates, in particular tetrafluoroborate (abbreviated BF4-); phosphates, in particular hexafluorophosphate (abbreviated PF6-); phosphinates and phosphonates, in particular alkylphosphonates; amides, in particular dicyanamide (abbreviated DCA-); aluminates, in particular tetrachloroaluminate (AlCl4 - ), halides (bromides, chlorides, iodides, etc., anions), cyanates, acetates (CH3COO - ), especially the trifluoroacetates; the sulfonates, especially methanesulfonate (CH3SO3-) or trifluoromethanesulfonate; the sulfates, especially ethyl sulfate or hydrogen sulfate, and mixtures thereof.

[0114] The term "organic salt" in the sense of the present invention is understood to mean more particularly any organic salt that is stable at the temperatures used during the synthesis of the block copolymer according to the method of the present invention. The skilled person can refer to the technical data sheets of the organic salts, which indicate the limit decomposition temperature of each organic salt.

[0115] In particular, examples of organic salts that can be used in the compositions according to the invention include organic salts based on ammonium cations, based on imidazolium cations or based on imidazolinium cations, based on pyridinium cations, based on dihydropyridinium cations, based on tetrahydropyridinium cations, based on pyrrolidinium cations, based on guanidine cations or based on phosphonium cations.

[0116] Organic salts based on ammonium cations include, for example, the following combinations: -N,N,N-trimethyl-N-propylammonium cation and bis(trifluoromethanesulfonyl)imide anion; - an N,N,N-trimethyl-N-butylammonium or N,N,N-trimethyl-N-hexylammonium cation and an anion selected from bromide, tetrafluoroborate, hexafluorophosphate, or bis(trifluoromethanesulfonyl)imide; -N,N,N-tributyl-N-methylammonium cation and iodide, bis(trifluoromethanesulfonyl)imide or dicyanamide anion; -tetraethylammonium cation and tetrafluoroborate anion; -(2-hydroxyethyl)trimethylammonium cation and dimethylphosphate anion; -di(2-hydroxyethyl)ammonium cation and trifluoroacetate anion; -N,N-di(2-methoxy)ethylammonium cation and sulfamate anion; -N,N-dimethyl(2-hydroxyethyl)ammonium cation and the 2-hydroxyacetate or trifluoroacetate anion; -N-ethyl-N,N-dimethyl(2-methoxyethyl)ammonium cation and bis(trifluoromethylsulfonyl)imide anion; -ethyldimethylpropylammonium cation and bis(trifluoromethylsulfonyl)imide anion; -Methyltrioctylammonium cation and bis(trifluoromethylsulfonyl)imide anion; -methyltrioctylammonium cation and the trifluoroacetate or trifluoromethylsulfonate anion; -tetrabutylammonium cation and bis(trifluoromethylsulfonyl)imide anion; -tetramethylammonium cation and bis[oxalato(2-)]borate or tris(pentafluoroethyl)trifluorophosphate anion.

[0117] Mention may also be made of organic salts based on imidazoles, such as di-, mono- or tri-substituted imidazoles, in particular those based on imidazolium or imidazolinium cations.

[0118] Examples include organic salts based on the imidazolium cation in combination with: -N-methylimidazolium cation and chloride anion; -1-ethyl-3-methylimidazolium cation and chloride, bromide, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, bis(trifluoromethanesulfonyl)imide, tetrachloroaluminate, ethyl or methylphosphonate, methanesulfonate, ethyl sulfate or ethylsulfonate anion; -1-butyl-3-methylimidazolium cation and the chloride, bromide, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, bis(trifluoromethanesulfonyl)imide, tetrachloroaluminate, acetate, hydrogensulfate, trifluoroacetate or methanesulfonate anion; -1,3-dimethylimidazolium cation and methylphosphonate anion; -1-propyl-2,3-dimethylimidazolium cation and bis(trifluoromethanesulfonyl)imide anion; -1-butyl-2,3-dimethylimidazolium cation and tetrafluoroborate or bis(trifluoromethanesulfonyl)imide anion; -1-hexyl-3-methylimidazolium cation and tetrafluoroborate, hexafluorophosphate, or bis(trifluoromethanesulfonyl)imide anion; -1-octyl-3-methylimidazolium cation and bis(trifluoromethanesulfonyl)imide anion; -1-ethanol-3-methylimidazolium cation and chloride, bromide, tetrafluoroborate, hexafluorophosphate, bis(trifluoromethanesulfonyl)imide or dicyanamide anion.

[0119] By way of example, mention may also be made of organic salts based on the pyridinium cation, such as: N-butyl-3-methylpyridinium bromide, N-butyl-4-methylpyridinium chloride, N-butyl-4-methylpyridinium tetrafluoroborate, N-butyl-3-methylpyridinium chloride, N-butyl-3-methylpyridinium dicyanamide, N-butyl-3-methylpyridinium methyl sulfate, 1-butyl-3-methylpyridinium tetrafluoroborate, N-butylpyridinium chloride, N-butyl ... pyridinium tetrafluoroborate, N-butylpyridinium trifluoromethylsulfonate, 1-ethyl-3-hydroxymethylpyridinium sulfate, N-hexylpyridinium bis(trifluoromethylsulfonyl)imide, N-hexylpyridinium trifluoromethanesulfonate, N-(3-hydroxypropyl)pyridinium bis(trifluoromethylsulfonyl)imide, N-butyl-3-methylpyridinium trifluoromethanesulfonate, or N-butyl-3-methylpyridinium hexafluorophosphate.

[0120] Examples include organic salts based on the pyrrolidinium cation, such as 1-butyl-1-methylpyrrolidinium chloride, 1-butyl-1-methylpyrrolidinium dicyanamide, 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate, 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl), 1-butyl-1-methylpyrrolidinium bis[oxalato(2-)]borate, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-butyl-1-methylpyrrolidinium dicyanamide, 1-butyl-1-methylpyrrolidinium trifluoroacet ... tris(trifluoromethylsulfonyl)imide, 1-butyl-1-methylpyrrolidinium tris(trifluoromethylsulfonyl), 1-butyl-1-methylpyrrolidinium tris(trifluoromethylsulfonyl), 1-butyl-1-methylpyrrolidinium tris(trifluoromethylsulfonyl), 1-butyl-1-methylpyrrolidinium tris(trifluoromethylsulfonyl), 1-butyl-1-methylpyrrolidinium tris(trifluoromethylsulfonyl), 1-butyl-1-methylpyrrolidinium tris(trifluoromethylsulfonyl), 1-butyl-1-methylpyrrolidinium tris(trifluoromethylsulfonyl), 1 trifluoromethanesulfonate, 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate, 1,1-dimethylpyrrolidinium iodide, 1-(2-ethoxyethyl)-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-hexyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-(2-methoxyethyl)-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-methyl-1-octylpyrrolidinium chloride, or 1-butyl-1-methylpyrrolidinium bromide.

[0121] Also included are organic salts that are combinations of: -1-ethyl-1-methylpyrrolidinium cation and bromide, tetrafluoroborate, hexafluorophosphate, or trifluoromethanesulfonate anion; -1-butyl-1-methylpyrrolidinium cation and chloride, bromide, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, bis(trifluoromethanesulfonyl)imide, dicyanamide, acetate, or hydrogen sulfate anion; -N-propyl-N-methylpyrrolidinium cation and bis(trifluoromethanesulfonyl)imide anion; -1-methyl-1-propylpiperidinium cation and bis(trifluoromethanesulfonyl)imide anion.

[0122] By way of example, mention may also be made of organic salts based on the guanidine cation, such as guanidine trifluoromethylsulfonate, guanidine tris(pentafluoroethyl)trifluorophosphate or hexamethylguanidine tris(pentafluoroethyl)trifluorophosphate.

[0123] Mention may be made of organic salts based on phosphonium cations, such as trihexyl(tetradecyl)phosphonium bis[oxalic acid(2-)]borate, trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)imide or trihexyl(tetradecyl)phosphonium tris(pentafluoroethyl)trifluorophosphate.

[0124] The above list of organic salts, cations and anions that can be involved in the composition of the organic salt that can be used according to the invention is given merely as an example, and is not exhaustive or limiting. Advantageously, the composition according to the invention further comprises at least one inorganic salt, i.e. an alkali metal salt or an alkaline earth metal salt, among which in particular lithium, sodium, potassium, magnesium, calcium, etc., with an organic acid (mono- or dicarboxylic acid containing 1 to 12 carbon atoms, such as formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, etc.), a sulfonic acid containing 1 to 20 carbon atoms, such as methanesulfonic acid, p-toluenesulfonic acid, thiocyanic acid, etc.) or a mineral acid (hydrohalic acid, such as hydrochloric acid or hydrobromic acid, perchloric acid, sulfuric acid, phosphoric acid, etc.), an alkali metal salt, and an alkaline earth metal salt. Examples of the lithium salt include lithium, potassium acetate, lithium chloride, acetate, calcium, magnesium chloride, sodium chloride, bromide, potassium bromide, magnesium, lithium perchlorate, bromide, potassium perchlorate or sodium perchlorate, potassium sulfate, potassium phosphate, and lithium thiocyanate.

[0125] Among them, halides, preferably lithium chloride, sodium chloride or potassium chloride, potassium acetate and potassium perchlorate are preferred. The amount of inorganic salt is generally within the range of 0.001% to 3%, preferably 0.01% to 2%, based on the weight of the composition.

[0126] The composition according to the invention may further comprise at least one additive selected from stabilizers, plasticizers, lubricants, natural or organic fillers, dyes, pigments, pearlescent agents, antimicrobial agents, flame retardants, antistatic agents, agents modifying the viscosity of the copolymer, toughening agents, antioxidants, UV stabilizers, flame retardants, mold release agents, impact modifiers, anti-shrinkage agents, blowing agents, nucleating agents and / or other additives or adjuvants already mentioned and well known to those skilled in the art of thermoplastic polymers.

[0127] Advantageously, the composition of the present invention further comprises at least one agent for improving surface conductivity selected from the following: moisture absorbents; fatty acids; lubricants; metals; metal films; metal powders; metal nanopowders; aluminosilicates; amines, such as quaternary amines; esters; fibers; carbon black; carbon fibers; carbon nanotubes; polyethylene glycol; inherently conductive polymers, such as polyaniline, polythiophene, polypyrrole derivatives; masterbatches; and mixtures thereof.

[0128] Another subject of the invention is the use of the compositions according to the invention for producing at least some of the following objects: industrial parts, automotive parts, safety accessories, signs, cornice lighting, information and advertising panels, showcases, sculptures, furniture, shop fittings, decorations, contact balls, dental prostheses, ophthalmic implants, membranes for hemodialysis, optical fibres, works of art, decorations, sculptures, lenses, in particular camera lenses, disposable camera lenses, printing media, in particular media for direct printing with UV inks for photographic images, window panes, sunroofs, vehicle headlamps, etc.

[0129] The transparent compositions of the present invention have improved antistatic properties due to the reduction in surface resistivity contributed by the PEBA copolymer, as explained in detail above. The compositions according to the present invention can be manufactured by any process well known to those skilled in the art of polymers, in particular by dry blending, by kneading at a temperature higher than the glass transition temperature of the various polymers added, or by shearing at a temperature substantially equal to the flow temperature of the various polymers added, in particular by calendaring, extrusion, or blending in solution.

[0130] Working Example The following examples are illustrative of the present invention but are not intended to be limiting thereof.

[0131] The copolymers shown in the table below are prepared by mixing the monomers in the melt.

[0132] The table indicates the weight content of the blocks present in the copolymer. TIFF2024528071000002.tif6017011=Units derived from polycondensation of undecane diacid MXD10 = Units derived from polycondensation of m-xylylenediamine and sebacic acid MXDI = Units derived from polycondensation of m-xylylenediamine and isophthalic acid PEG: Polyethylene glycol RI = Refractive index measured using an Abbe refractometer according to the ISO 489-1999 standard *The aromatic unit content of copolymer 3 is determined as follows: Mm(MXD) / Mm(MXD)+Mm(10)×70=28.2%

Claims

1. A block copolymer comprising at least one polyamide block and at least one polyether block, - the polyamide block contains at least one unit of the formula XDY, wherein, XD represents a unit derived from m-xylylenediamine, p-xylylenediamine and mixtures thereof, preferably a unit derived from m-xylylenediamine, Y represents a unit derived from a linear or branched aliphatic, cycloaliphatic or aromatic dicarboxylic acid containing 4 to 36 carbon atoms, - the polyether block contains ethylene oxide units in a content of 20% or more based on the total weight of the copolymer, - the content of aromatic units is 20% to 80% based on the total weight of the copolymer A copolymer, characterized by the above.

2. The copolymer according to claim 1, characterized by showing a refractive index of 1.51 or more.

3. The copolymer according to claim 1, wherein the dicarboxylic acid (Y) is an aliphatic diacid having 6 to 36 carbon atoms, preferably 6 to 18 carbon atoms, more preferably 9 to 18 carbon atoms, in particular, 1,10-decanedicarboxylic acid (represented by 10), 1,11-undecanedicarboxylic acid (represented by 11), 1,12-dodecanedicarboxylic acid (represented by 12), 1,14-tetradecanedicarboxylic acid (represented by 14) and 1,18-octadecanedicarboxylic acid (represented by 18), and an aromatic dicarboxylic acid having 6 to 36 carbon atoms, in particular terephthalic acid (represented by T), isophthalic acid (represented by I), naphthalenedicarboxylic acid (represented by N) and 2,5-furandicarboxylic acid.

4. The copolymer according to claim 1, wherein the polyamide block contains at least one additional unit of the formula Z [wherein Z represents a unit derived from an amino acid unit, a lactam unit, or a unit obtained by polycondensation of a unit corresponding to the formula (Ca diamine)·(Cb dicarboxylic acid) (wherein Ca and Cb can each contain 4 to 36 carbon atoms)].

5. The copolymer according to claim 1, wherein the polyamide block is selected from XD1, XDT, XD10 / XDI, XD10 / XDT, 11 / XDI, 11 / XDT, XD10 / XDI / XDT or 11 / XDI / XDT.

6. The copolymer according to claim 1, wherein the ethylene oxide units are derived from polyethylene glycol or a polyetheramine containing ethylene oxide units.

7. The copolymer according to claim 1, selected from PAMXD10-PEG, PAMXD11-PEG, PAPXD10-PEG, PAPXD11-PEG, PAMXDT-PEG, PAMXDI-PEG, PAPXDT-PEG, PAPXDI-PEG and / or mixtures thereof.

8. (a) At least one block copolymer comprising at least one polyamide block and at least one polyether block, wherein the polyamide block comprises at least one unit of formula AY, in which -A represents a unit derived from a linear or branched aliphatic, cycloaliphatic or alkyl aromatic diamine, -Y represents a unit derived from the dicarboxylic acid according to any one of claims 1 to 3, -the content of the polyether block of ethylene oxide units is 30% or more based on the total weight of the copolymer, -the content of aromatic units is 20% to 80% based on the total weight of the copolymer, at least one block copolymer, and (b) a transparent thermoplastic polymer matrix comprising at least one thermoplastic polymer having a refractive index of 1.51 or more A transparent antistatic polymer composition comprising.

9. The composition according to claim 8, wherein the block copolymer has a refractive index of 1.51 or more.

10. The diamine A is selected from butanediamine (represented by 4), pentanediamine (represented by 5), hexanediamine (represented by 6), heptanediamine (represented by 7), octanediamine (represented by 8), nonanediamine (represented by 9), decanediamine (represented by 10), undecanediamine (represented by 11), dodecanediamine (represented by 12), tridecanediamine (represented by 13), tetradecanediamine (represented by 14), hexadecanediamine (represented by 16), octadecanediamine (represented by 18), octadecenediamine (represented by 18), eicosanediamine (represented by 20), docosanediamine (represented by 22), and diamines obtained from fatty acids, bis(3-methyl-4-aminocyclohexyl)methane (represented by BMACM or MACM), bis(p-aminocyclohexyl)methane (denoted as PACM) and isopropylidene di(cyclohexylamine) (denoted as PACP), m-xylylenediamine, p-xylylenediamine, and mixtures thereof, preferably m-xylylenediamine, the composition according to claim 8.

11. The ethylene oxide units are derived from polyethylene glycol or from a polyetheramine containing ethylene oxide units, the composition according to claim 8.

12. The thermoplastic polymer of the matrix is selected from polycarbonate (PC), polystyrene, polyethylene terephthalate (PET), polyethylene terephthalate glycol (PETG), polysulfone, acrylonitrile-butadiene-styrene (ABS), styrene-acrylonitrile (SAN), acrylonitrile-styrene-acrylate (ASA), copolymers thereof and alloys thereof, the composition according to claim 8.

13. The polyamide block further comprises at least one unit obtained by polycondensation of amino acid or lactam units, the composition according to claim 8. ​ ​ ​ The content of the aromatic unit is 35% to 60% based on the total weight of the copolymer. The composition according to claim 8.

15. The composition according to claim 8, comprising an organic salt.

16. Use of the copolymer according to claim 1 as an antistatic additive.