Polyamide compositions comprising reinforcing fibers and having high modulus stability, and uses thereof

Abstract

To provide use of a polyamide mixture for preparing a semi-crystalline composition the modulus of which does not vary by more than 25% within the temperature range from 10°C to 40°C.SOLUTION: Provided is use of a mixture of at least one semi-crystalline aliphatic polyamide and at least one amorphous polyamide, wherein the at least one semi-crystalline aliphatic polyamide is obtained by polycondensation: of at least one C6-C18, preferably C10-C18, more preferably C10-C12 amino acid, or at least one C6-C18, preferably C10-C18, more preferably C10-C12 lactam, or at least one C4-C36, preferably C5-C18, preferably C5-C12, more preferably C10-C12 diamine Ca, with at least one C4-C36, preferably C6-C18, preferably C6-C12, more preferably C10-C12 dicarboxylic acid Cb.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present patent application relates to the use of semi-crystalline aliphatic polyamides and amorphous polyamides for the preparation of compositions having high modulus stability under the effects of temperature and humidity, methods for their preparation, and said compositions. [Background technology]

[0002] Many applications in the E / E sector require the use of high modulus polymer materials, e.g., for televisions, digital cameras, digital games, phone components, digital tablets, drones, printers, or computer components. The modulus of a material is indeed a crucial factor for enabling low weight, since it allows the thickness of the part to be reduced while maintaining high stiffness. A distinction is made between different moduli (e.g., tensile modulus, flexural modulus, etc.). These moduli can be affected by the temperature and moisture level of the sample.

[0003] It is also important that stiffness be little affected by changes in temperature or water content of the material. Indeed, modulus stability is also an important factor for subsequent use or to ensure ease of assembly where parts may be assembled where temperatures and / or humidity may be high.

[0004] Therefore, there is a need for polyamide compositions whose modulus remains stable over the range of temperatures and / or humidity to which they are exposed, particularly during component assembly and subsequent device operation. Preferably, the modulus should be stable at temperatures between 10°C and 40°C, particularly in the temperature range of 0°C to 40°C, and especially in the temperature range of -10°C to 40°C, for compositions having variable water content (such as resulting from conditioning the composition in an atmosphere where humidity measurements can vary from 0 to 100% or in liquid water).

[0005] In addition, the polyamide composition must have a moderate molding temperature and crystallize quickly enough to allow processing times, especially cycle times, suitable for industrial processes.

[0006] However, aliphatic polyamides generally lose a significant amount of stiffness at elevated temperatures due to the presence of a certain amount of water, especially if these polyamides have been pre-conditioned in a humid atmosphere.

[0007] From application WO 2018 / 073536 it is known that semi-aromatic polyamides, in particular MXDZ polyamides, are used in blends with aliphatic polyamides, in particular semi-crystalline polyamides, containing glass fibres with a circular cross section in order to limit the warpage of the resulting compositions.

[0008] It is also known from international application WO 2018 / 073537 that circular cross-section glass fibers are used in blends comprising at least one MXDZ polyamide and at least one aliphatic polyamide, in particular a semi-crystalline polyamide, to improve the mechanical properties, in particular the elongation at break, of the composition after processing, in particular by injection molding or compression molding.

[0009] Furthermore, document WO 10 / 015785 describes copolyamides comprising at least two different A / XT units, characterized in that the copolyamide has an amine chain end content of 20 μeq / g or more, an acid chain end content of 100 μeq / g or less, and a non-reactive chain end content of 20 μeq / g or more. The copolyamide may also contain additives, in particular reinforcing fibers, which may be glass fibers.

[0010] Document WO 10 / 015786 describes copolyamides containing at least two A / 10T units, characterized in that they have a polymolecularity index, denoted Ip, of less than or equal to 3.5, determined by gel permeation chromatography.

[0011] International application WO2014 / 195226 describes a composition for electronic mobile devices comprising at least 20% of at least one polymer and at least 20% of glass fibers having a non-circular cross section and a modulus of elasticity of at least 76 GPa determined according to ASTM C1557-03.

[0012] None of these prior art documents mention the stability of the modulus as a function of temperature and preconditioning of the composition.

[0013] This leaves the problem of providing a polyamide-based formulation that combines a high modulus that is stable over a wide temperature range, even when the composition is saturated with water, with good injection moldability. Summary of the Invention

[0014] It is therefore an object of the present invention to provide amorphous semi-crystalline polyamide blends for the preparation of compositions with high modulus stability under the effects of temperature and humidity.

[0015] Also according to a first aspect, one subject of the present invention is the use of a mixture of at least one semicrystalline aliphatic polyamide and at least one amorphous polyamide for preparing a semicrystalline composition whose modulus does not vary by more than 25% in the temperature range from 10°C to 40°C, in particular in the temperature range from 0°C to 40°C, and more particularly in the temperature range from -10°C to 40°C, wherein the semicrystalline aliphatic polyamide At least one C6-C 18 , with priority given to C 10 ~C 18 , more preferentially C 10 ~C 12 amino acids, or At least one C6-C 18 , with priority given to C 10 ~C 18 , more preferentially C 10 ~C 12 lactam, or At least one C4-C36 , priority is given to C5C 18 , priority is given to C5C 12 , more preferentially C 10 ~C 12 and at least one C4-C 36 , with priority given to C6~C 18 , with priority given to C6~C 12 , more preferentially C 10 ~C 12 Aliphatic dicarboxylic acid Cb and It is used to obtain the above-mentioned polycondensation.

[0016] Advantageously, the Tg of the semi-crystalline composition, determined by DMA according to ISO 6721-11:2019, exhibits an increase of at least 5°C, preferentially at least 10°C and more preferentially at least 15°C, relative to the initial Tg of the semi-crystalline polyamide before mixing.

[0017] The Tg of the semi-crystalline composition described above is determined in a dry or moist atmosphere, advantageously in a saturated atmosphere of water at 65°C.

[0018] Advantageously, the Tg of the semi-crystalline composition, as determined by DMA, is between 5°C and 120°C, advantageously between 10°C and 120°C, more advantageously between 15°C and 120°C.

[0019] Tg is determined by dynamic mechanical analysis (DMA) according to ISO standard 6721-11:2019.

[0020] The inventors have unexpectedly found that by selecting a semi-crystalline aliphatic polyamide and at least one amorphous polyamide in specific proportions, it is possible to prepare compositions which not only exhibit a stable modulus under the effects of temperature and humidity, which does not fluctuate by more than 25% in the temperature range from 10°C to 40°C, in particular in the temperature range from 0°C to 40°C, and especially in the temperature range from -10°C to 40°C, but also whose processing is facilitated by low molding temperatures, in particular below 100°C, preferably below 90°C, more preferentially below 80°C, and during which short cycle times, in particular below 50 seconds, are carried out.

[0021] The inventors have also found that this selection of a blend of semi-crystalline aliphatic polyamide with at least one amorphous polyamide in specific proportions increases the Tg of the composition above that of the semi-crystalline aliphatic polyamide alone, while maintaining the semi-crystalline character of the composition. DETAILED DESCRIPTION OF THE INVENTION

[0022] The nomenclature used to define polyamides is set out in ISO standard 1874-1:2011 "Plastiques--Materiaux polyamides (PA) pour moulage et extrusion--Partie 1:Designation", especially page 3 (Tables 1 and 2), and is well known to those skilled in the art.

[0023] Semicrystalline copolyamide, in the sense of the present invention, denotes a polyamide having a glass transition temperature determined by dynamic mechanical analysis (DMA) according to ISO standard 6721-11:2019, a melting temperature (Tm) determined according to ISO standard 11357-3:2013, and a crystallization enthalpy in DSC measured according to ISO standard 11357-3 of 2013, during a cooling step at a rate of 20 K / min, of more than 30 J / g, preferably more than 35 J / g.

[0024] Amorphous polyamides, in the sense of the present invention, refer to polyamides that have only a glass transition temperature (no melting temperature (Tm)) or that have a glass transition temperature and a melting point but have very little crystallinity, the crystallization enthalpy during a cooling step at a rate of 20 K / min, measured according to standard ISO 11357-3:2013, being less than 30 J / g, in particular less than 20 J / g, preferably less than 15 J / g.

[0025] In one embodiment, the semi-crystalline aliphatic polyamide is linear.

[0026] In one embodiment, the semi-crystalline aliphatic polyamide is a homopolyamide, in particular a semi-crystalline linear aliphatic homopolyamide.

[0027] Advantageously, the amorphous polyamide used in the invention has a Tg of 100 to 200°C, in particular 120 to 190°C.

[0028] When the at least one semi-crystalline aliphatic polyamide is obtained from the polycondensation of at least one lactam, the at least one lactam is selected from the group consisting of C6 to C 18 Lactams, preferentially C 10 ~C 18 , more preferentially C 10 ~C 12 C6 to C 12 Lactams are especially caprolactam, decanolactam, undecanolactam and lauryllactam.

[0029] When the at least one semi-crystalline aliphatic polyamide results from the polycondensation of at least one lactam, the at least one lactam may therefore comprise a single lactam or several lactams.

[0030] Advantageously, the at least one semi-crystalline aliphatic polyamide results from the polycondensation of a single lactam, the lactam being chosen from lauryllactam and undecanolactam, advantageously lauryllactam.

[0031] When the at least one semi-crystalline aliphatic polyamide is obtained from the polycondensation of at least one amino acid, the at least one amino acid is selected from the group consisting of C6 to C 18 Amino acids, preferentially C 10 ~C 18 , more preferentially C 10 ~C 12 may be selected from:

[0032] Amino acids C6 to C 12are, inter alia, 6-aminohexanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 10-aminoundecanoic acid, 12-aminododecanoic acid, and 11-aminoundecanoic acid, and derivatives thereof, inter alia, N-heptyl-11-aminoundecanoic acid.

[0033] When the at least one semi-crystalline aliphatic polyamide results from the polycondensation of at least one amino acid, the at least one amino acid may therefore comprise a single amino acid or several amino acids.

[0034] Advantageously, the semi-crystalline aliphatic polyamide results from the polycondensation of a single amino acid, the amino acid being chosen from 11-aminoundecanoic acid and 12-aminododecanoic acid, advantageously 11-aminoundecanoic acid.

[0035] The at least one semi-crystalline aliphatic polyamide is at least one C4-C 36 , with priority given to C5~C 18 , with priority given to C5~C 12 , more preferentially C 10 ~C 12 Diamine Ca and at least one C4-C 36 , with priority given to C6~C 18 , with priority given to C6~C 12 , more preferentially C 10 ~C 12 If it results from polycondensation with a diacid Cb, the at least one diamine Ca is an aliphatic diamine and the at least one diacid Cb is an aliphatic diacid.

[0036] The diamines may be linear or branched. Advantageously, the diamines are linear.

[0037] The at least one C4 to C 36The diamine Ca can be chosen in particular from 1,4-butanediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine, 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,16-hexadecamethylenediamine, and 1,18-octadecamethylenediamine, octadecenediamine, eicosanediamine, docosanediamine, and diamines obtained from fatty acids.

[0038] Advantageously, the at least one diamine Ca is a C5-C 18 and is selected from 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine, 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,16-hexadecamethylenediamine, and 1,18-octadecamethylenediamine.

[0039] Advantageously, the at least one C5-C 12 The Ca diamine is chosen in particular from 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, and 1,12-dodecamethylenediamine.

[0040] Advantageously, the diamine Ca used is C 10 ~C 12 It is a diamine, in particular chosen from 1,10-decamethylenediamine, 1,11-undecamethylenediamine, and 1,12-dodecamethylenediamine.

[0041] The at least one C4 to C 36 The dicarboxylic acid Cb may be selected from succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and diacids obtained from fatty acids.

[0042] The diacids may be linear or branched. Advantageously, the diacids are linear.

[0043] Advantageously, the at least one Cb dicarboxylic acid is a C6-C 18 and is selected from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, and octadecanedioic acid.

[0044] Advantageously, the at least one Cb dicarboxylic acid is a C6-C 12 and can be selected from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid.

[0045] Advantageously, the at least one Cb dicarboxylic acid is C 10 ~C 12 and is selected from sebacic acid, undecanedioic acid, and dodecanedioic acid.

[0046] When the semi-crystalline aliphatic polyamide results from the polycondensation of at least one diamine Ca with at least one dicarboxylic acid Cb, it may therefore comprise a single diamine or several diamines and a single dicarboxylic acid or several dicarboxylic acids.

[0047] Advantageously, the semi-crystalline aliphatic polyamide results from the polycondensation of a single diamine Ca with a single dicarboxylic acid Cb.

[0048] If the at least one amorphous polyamide is a homopolyamide of formula XY or a copolyamide of formula A / XY, XY is a mixture of at least one alicyclic diamine (X) and at least one C4-C 36 , with priority given to C6~C 18 , with priority given to C6~C 12 , more preferentially C 10 ~C 12 A is a repeating unit obtained by polycondensation with an aliphatic dicarboxylic acid (Y) or at least one aromatic dicarboxylic acid (Y), and A is at least one C6-C 18 , with priority given to C 10 ~C 18 , more preferentially C 10 ~C 12 amino acids, or At least one C6-C 18 , with priority given to C 10 ~C 18 , more preferentially C 10 ~C 12 lactam, or At least one C4-C 36 , with priority given to C5~C 18 , with priority given to C5~C 12 , more preferentially C 10 ~C 12 Ca diamine and at least one C4-C 36 , with priority given to C6~C 18 , with priority given to C6~C 12 , more preferentially C 10 ~C 12 Dicarboxylic acid Cb and It is a repeating unit obtained by polycondensation of the following.

[0049] The alicyclic diamine (X) may be 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, or 3,3'-dimethyl-4,4'-diamino-dicyclohexyl-methane, commonly referred to as "BMACM" or "MACM". and p-bis(aminocyclohexyl)-methane (hereinafter referred to as B), commonly referred to as "PACM" (hereinafter referred to as P), particularly Dicykan®, isopropylidenedi(cyclohexylamine), commonly referred to as "PACP", isophorone-diamine (hereinafter referred to as IPD), and 2,6-bis(aminomethyl)norbornane, commonly referred to as "BAMN", as well as bis(aminomethyl)cyclohexane "BAC", particularly 1,3-BAC, or particularly 1,4-BAC.

[0050] Advantageously, the cycloaliphatic diamine (X) is chosen from bis-(3-methyl-4-aminocyclohexyl)-methane or 3,3'-dimethyl-4,4'-diamino-dicyclohexyl-methane (hereinafter designated B), commonly called (BMACM) or (MACM), bis(p-aminocyclohexyl)-methane (hereinafter designated P), commonly called (PACM), and bis(aminomethyl)cyclohexane (BAC), in particular 1,3-BAC, or especially 1,4-BAC.

[0051] A, Ca, and Cb are as defined above.

[0052] (Y) is at least one C4-C 36 , with priority given to C6~C 18 , with priority given to C6~C 12 , more preferentially C 10 ~C 12 When Cb is an aliphatic dicarboxylic acid, it is as defined for Cb.

[0053] When (Y) is at least one aromatic dicarboxylic acid (Y), it is advantageously chosen from terephthalic acid (denoted T), isophthalic acid (denoted I) and 2,6-naphthalenedicarboxylic acid (denoted N), or mixtures thereof; in particular from terephthalic acid (denoted T), isophthalic acid (denoted I), or mixtures thereof.

[0054] The modulus of elasticity of the composition varies with temperature, generally decreasing with increasing temperature.

[0055] The expression "the modulus of elasticity does not vary by more than 25% in the temperature range of 10°C to 40°C, particularly in the temperature range of 0°C to 40°C, and especially in the temperature range of -10°C to 40°C" means that the modulus of elasticity of the same composition does not vary by more than 25% in these temperature ranges of 10°C to 40°C, 0°C to 40°C, and -10°C to 40°C, whether it is the flexural modulus or tensile modulus measured after the same conditioning (in a dry or humid atmosphere).

[0056] Advantageously, the modulus of the composition does not vary by more than 35% in the temperature range from -10°C to 50°C.

[0057] The expression "the modulus of elasticity does not vary by more than 35% in the temperature range of -10°C to 50°C" means that the modulus of elasticity of the same composition does not vary by more than 35% in this range of -10°C to 50°C, whether it is the flexural modulus or the tensile modulus measured after the same conditioning (in a dry or humid atmosphere).

[0058] More advantageously, the modulus of the composition does not vary by more than 40% over the temperature range of -10°C to 60°C.

[0059] The expression "the modulus of elasticity does not vary by more than 40% in the temperature range of -10°C to 60°C" means that the modulus of elasticity of the same composition does not vary by more than 40% in the range of -10°C to 60°C, whether it is the flexural modulus or the tensile modulus measured after the same conditioning (in a dry or humid atmosphere).

[0060] The term "wet conditioning" means after saturation of the liquid in water at 65°C.

[0061] In other words, for compositions conditioned under the same dry or humid atmospheric conditions, -10 is the modulus of elasticity measured at -10°C, and M T is the modulus measured at temperature T, ((M -10 -M T ) / M -10 ) × 100≦25% (where T varies from −10 to 40°C).

[0062] In one embodiment, the modulus of elasticity is measured according to ISO 178:2010 as defined above and corresponds to the flexural modulus.

[0063] In another embodiment, the modulus of elasticity is measured according to ISO 2:2012 as defined above and corresponds to the tensile modulus.

[0064] In another embodiment, the modulus corresponds to both the flexural modulus and the tensile modulus, both measured as previously defined herein.

[0065] Advantageously, the change in flexural modulus measured at 20°C on a sample saturated in water at 65°C and on a dry sample at 20°C is not more than 15%, in particular not more than 7%, both measurements being made in accordance with ISO 178:2010. In other words, (M sec -M sat )×100 / M sec ≦15%.

[0066] In one embodiment, the at least one amorphous polyamide is a homopolyamide of formula XY or a copolyamide of formula A / XY, where XY is a mixture of at least one cycloaliphatic diamine (X) and at least one C4-C 36 , with priority given to C6~C 18, with priority given to C6~C 12 , more preferentially C 10 ~C 12 A is a repeating unit obtained by polycondensation with an aliphatic dicarboxylic acid (Y) or at least one aromatic dicarboxylic acid (Y), and A is at least one C6-C 18 , with priority given to C 10 ~C 18 , more preferentially C 10 ~C 12 amino acids, or At least one C6-C 18 , with priority given to C 10 ~C 18 , more preferentially C 10 ~C 12 lactam, or At least one C4-C 36 , with priority given to C5~C 18 , with priority given to C5~C 12 , more preferentially C 10 ~C 12 Ca diamine and at least one C4-C 36 , with priority given to C6~C 18 , with priority given to C6~C 12 , more preferentially C 10 ~C 12 Dicarboxylic acid Cb and It is a repeating unit obtained by polycondensation of the following.

[0067] In a first variant, the at least one amorphous polyamide is a copolyamide of formula A / XY, where A is obtained by polycondensation of at least one amino acid or by polycondensation of at least one lactam, X is selected from B or P or BAC, and Y is terephthalic acid and / or isophthalic acid.

[0068] Advantageously, in this first variant, A / XY is chosen from the units 11 / BI / BT, 12 / BI / BT, 11 / BACI / BACT, 12 / BACI / BACT, 11 / BACI, 12 / BACI, 11 / PI / PT, 12 / PI / PT, and mixtures thereof.

[0069] In a second variant, the at least one amorphous polyamide is a copolyamide of formula A / XY, where A is obtained by polycondensation of at least one amino acid or by polycondensation of at least one lactam, X is selected from B or P and Y is sebacic acid or dodecanedioic acid.

[0070] Advantageously, in this second variant, A / XY is chosen from the units 11 / B10, 11 / B12, 11 / P10, 11 / P12, 12 / B10, 12 / B12, 12 / P10, 12 / P12, and mixtures thereof.

[0071] In a third variant, the at least one amorphous polyamide is a copolyamide of formula A / XY, where A is obtained by polycondensation of at least one diamine Ca with at least one dicarboxylic acid Cb, X is selected from B or P and Y is sebacic acid or dodecanedioic acid.

[0072] Advantageously, in this third variant, A / XY is chosen from the units 1010 / B10, 1010 / B12, 1010 / P10, 1010 / P12, 1012 / B10, 1012 / B12, 1012 / P10, 1012 / P12, 1210 / B10, 1210 / B12, 1210 / P10, 1210 / P12, 1212 / B10, 1212 / B12, 1212 / P10, 1212 / P12, and mixtures thereof.

[0073] In a fourth variant, the at least one amorphous polyamide is a homopolyamide of formula XY, where X is selected from B or P and Y is sebacic acid or dodecanedioic acid.

[0074] Advantageously, in this fourth variant, XY is chosen from one of the units B10, B12, P10, P12, and mixtures thereof.

[0075] In one embodiment, the proportion by weight of the amorphous polyamide is 10 to 45%, preferentially 15 to 35% by weight, more preferentially 20 to 30% by weight, relative to the sum by weight of the at least one semi-crystalline polyamide and the at least one amorphous polyamide.

[0076] In another embodiment, the present invention relates to the use of a mixture of at least one semi-crystalline aliphatic polyamide and at least one amorphous polyamide for preparing a semi-crystalline composition as defined herein before, said composition comprising 35 to 75 wt. % reinforcing fibers, in particular 35 to 65 wt. % reinforcing fibers.

[0077] The composition according to the invention may comprise short or short fibrous reinforcing fibers.

[0078] Glass beads are excluded from the definition of reinforcing fibers.

[0079] Preferably the fibres are short fibres and, prior to use in the composition, have a length of between 2 and 13 mm, preferably between 3 and 8 mm.

[0080] These short reinforcing fibers are - natural fibers, mineral fibres, having a melting temperature Tm' higher than the melting temperature Tm of the semicrystalline polyamide of the invention and higher than the application temperature; - polymeric fibers or polymer fibres having a melting temperature Tm', or if not Tm', a glass transition temperature Tg', higher than the melting temperature Tm of the semicrystalline polyamide constituting the matrix of the thermoplastic resin material and higher than the application temperature, - or a mixture of the above-cited fibers can be selected from.

[0081] Examples of mineral fibres suitable for the present invention are carbon fibres, including fibres of nanotubes or carbon nanotubes (CNTs), carbon nanofibres or graphene; glass fibres, in particular silica fibres such as types D, E, R, S2 or T; boron fibres; ceramic fibres, in particular silicon carbide fibres, boron carbide fibres, boron carbonitride fibres, silicon nitride fibres, boron nitride fibres, basalt fibres or basalt-based fibres; fibres or filaments containing metals and / or alloys thereof; metal oxide fibres, in particular fibres of alumina (Al2O3); metallised fibres, such as metallised glass fibres and metallised carbon fibres, or mixtures of the previously cited fibres.

[0082] More particularly, these fibers can be chosen from: the mineral fibres may be chosen from carbon fibres, carbon nanotube fibres, glass fibres, in particular of type D, E, R, S2 or T, boron fibres, ceramic fibres, in particular silicon carbide fibres, boron carbide fibres, boron carbonitride fibres, silicon nitride fibres, boron nitride fibres, basalt fibres or basalt-based fibres; fibres or filaments containing metals and / or their alloys, fibres containing metal oxides such as Al2O3, metallised fibres, such as metallised glass fibres and metallised carbon fibres, or mixtures of the above-mentioned fibres; and - subject to the above conditions previously cited, the polymer or polymeric fibers are chosen from: - thermosetting polymer fibres, more particularly chosen from: unsaturated polyesters, epoxy resins, vinyl esters, phenolic resins, polyurethanes, cyanoacrylates and polyimides such as bis-maleimide resins, aminoplasts obtained from the reaction of amines such as melamine with aldehydes such as glyoxal or formaldehyde; - fibers of thermoplastic polymers, more particularly chosen from: polyethylene terephthalate (PET), polybutylene terephthalate (PBT); - polyamide fibers; - aramid fibers (such as Kevlar®) and aromatic polyamides such as those having one of the formulas: PPD.T, MPD.I, PAA and PPA, where PPD and MPD are respectively p- and m-phenylenediamine, PAA is polyarylamide and PPA is polyphthalamide; - Fibers of polyamide block copolymers such as polyamide / polyether, and fibers of polyaryletherketones (PAEK) such as polyetheretherketone (PEEK), polyetherketoneketone (PEKK), and polyetherketoneetherketoneketone (PEKEKK).

[0083] Preferred short reinforcing fibers are short fibers selected from carbon fibers, including metallized fibers, glass fibers, including metallized glass fibers such as E, R, S2 or T, aramid fibers (such as Kevlar®), or polyaryletherketone (PAEK) fibers, such as aromatic polyamides, polyetheretherketone (PEEK), polyetherketoneketone (PEKK) fibers, polyetherketoneetherketoneketone (PEKEKK) fibers, or mixtures thereof.

[0084] More particularly, the natural fibres are chosen from flax, castor, wood, sisal, kenaf, coconut, hemp and jute fibres.

[0085] Glass fibers within the meaning of the present invention are understood to be any glass fibers, in particular those described by Frederick T. Wallenberger, James C. Watson, and Hong Li, PPG Industries Inc. (ASM Handbook, Vol. 21: Composites (#06781G), 2001 ASM International).

[0086] The reinforcing fibers are - have a circular cross section with a diameter between 4 μm and 25 μm, preferably between 4 μm and 15 μm, - have a non-circular cross section with an L / D ratio (L representing the largest dimension of the cross section of the fiber and D representing the smallest dimension of the cross section of said fiber) between 2 and 8, in particular between 2 and 4. L and D can be measured by scanning electron microscopy (SEM).

[0087] Advantageously, the reinforcing fibers are chosen from glass fibers, carbon fibers, and mixtures thereof.

[0088] Advantageously, the reinforcing fibers are chosen from glass fibers with a non-circular cross section, glass fibers with a circular cross section, carbon fibers, and mixtures thereof.

[0089] Advantageously, the reinforcing fibers are selected from glass fibers with a non-circular cross section, glass fibers with a circular cross section, and mixtures thereof.

[0090] Advantageously, the reinforcing fibers are glass fibers with a circular cross section.

[0091] In another embodiment, the composition comprises, in addition to the semi-crystalline aliphatic polyamide, the amorphous polyamide, and the reinforcing fibers: - 0 to 10% by weight of at least one impact modifier, - 0 to 30% by weight of at least one filler, and - 0 to 10% by weight of at least one superplasticizer, and - 0 to less than 2% by weight, preferably 0.5 to less than 2% by weight of additives wherein the sum of the semi-crystalline aliphatic polyamide, the amorphous polyamide, the reinforcing fibers, the impact modifier, the filler, the flow agent, and the additives equals 100%.

[0092] In yet another embodiment, the composition comprises a semi-crystalline aliphatic polyamide, an amorphous polyamide, and reinforcing fibers, and - 0 to 10% by weight of at least one impact modifier; - 0 to 30% by weight of at least one filler; and - 0 to 10% by weight of at least one superplasticizer; and - from 0 to less than 2% by weight, preferably from 0.5 to less than 2% by weight, of additives, The sum of the semi-crystalline aliphatic polyamide, amorphous polyamide, reinforcing fibers, impact modifiers, fillers, flow agents, and additives equals 100%.

[0093] In another embodiment, the composition comprises, in addition to the semi-crystalline aliphatic polyamide, the amorphous polyamide, and the reinforcing fibers: - 0 to 10% by weight of at least one impact modifier; - 1 to 30% by weight of at least one filler; and - 0 to 10% by weight of at least one superplasticizer; and - containing from 0 to less than 2% by weight, preferably from 0.5 to less than 2% by weight, of additives, The sum of the semi-crystalline aliphatic polyamide, amorphous polyamide, reinforcing fibers, impact modifiers, fillers, flow agents, and additives equals 100%.

[0094] In yet another embodiment, the composition comprises a semi-crystalline aliphatic polyamide, an amorphous polyamide, a reinforcing fiber, and - 0 to 10% by weight of at least one impact modifier; - 1 to 30% by weight of at least one filler; and - 0 to 10% by weight of at least one superplasticizer; and - from 0 to less than 2% by weight, preferably from 0.5 to less than 2% by weight, of additives, The sum of the semi-crystalline aliphatic polyamide, amorphous polyamide, reinforcing fibers, impact modifiers, fillers, flow agents, and additives equals 100%.

[0095] Advantageously, the proportion of fillers in these compositions is between 5 and 30% by weight, in particular between 10 and 30% by weight and preferentially between 15 and 30% by weight.

[0096] In one embodiment, the proportion of fillers in these compositions is between 0 and 28% by weight, in particular between 1 and 28% by weight, between 5 and 28% by weight, in particular between 10 and 28% by weight and preferentially between 15 and 28% by weight.

[0097] The expression "impact modifier" means a polyolefin-based polymer, in particular a polyolefin, having a flexural modulus of less than 100 MPa, measured according to standard ISO 178:2010 (23°C RH50), and a Tg of less than 0°C (measured according to standard 11357-2:2013, at the level of the inflection point of the DSC thermogram).

[0098] The impact modifier may also be a PEBA block polymer (polyether block amide) having a flexural modulus of less than 200 MPa.

[0099] The impact modifier may also be a SEBS polyolefin.

[0100] The composition may further comprise one or more impact modifiers as defined above, the presence of which can impart greater ductility to the article produced.

[0101] The polyolefin of the impact modifier may be a functionalized polyolefin or a non-functionalized polyolefin, or may include both in a blend.

[0102] When the polyolefin is functionalized, some or all of the polyolefin has functional groups selected from carboxylic acid, carboxylic anhydride, and epoxide functional groups. The polyolefin may be selected, in particular, from ethylene and propylene copolymers (EPR) having elastomeric properties, ethylene-propylene-diene copolymers (EPDM) having elastomeric properties, and ethylene / alkyl (meth)acrylate copolymers, higher ethylene-alkene copolymers, in particular ethylene-octene copolymers, and ethylene-alkyl acrylate-maleic anhydride terpolymers.

[0103] Peba (polyether block amides) are copolymers containing polyamide and polyether blocks. They may also contain ester functional groups, in particular ester functional groups resulting from the condensation reaction of the terminal carboxyl groups of the polyamide blocks with the hydroxyl functional groups of the polyether blocks. Peba is marketed, in particular, by Arkema under the brand name Pebax®.

[0104] Advantageously, the impact modifier is chosen from Fusabond® F493, Pebax®, in particular Pebax® 40R53 SP01, Lotader®, Exxelor® VA1803 or VA1801, Orevac® IM800, or mixtures thereof, in which case they are in a ratio ranging from 0.1 / 99.9 to 99.9 / 0.1.

[0105] The impact modifier may also be a core-shell impact modifier, also referred to as a core-shell polymer. "Core-shell impact modifiers" exist in the form of fine particles having an elastomer core and at least one thermoplastic resin shell, the particle size of which is generally less than a micrometer, advantageously between 150 nm and 500 nm inclusive. Core-shell impact modifiers have an acrylic or butadiene base.

[0106] Several different impact modifiers may be present in the composition.

[0107] According to one particular embodiment, the content of impact modifier relative to the total weight of the composition may vary from 0 to 10% by weight, advantageously from 1 to 10% by weight.

[0108] According to one embodiment, the composition comprises from 1 to 8% by weight, in particular from 2 to 5% by weight, of impact modifier relative to the total weight of the composition.

[0109] In other embodiments, the content of impact modifier in the composition may vary from 1 to 2 wt%; or 2 to 3 wt%; or 3 to 4 wt%; or 4 to 5 wt%; or 5 to 6 wt%; or 6 to 7 wt%; or 7 to 8 wt%; or 8 to 9 wt%; or 9 to 10 wt%.

[0110] About fillers The composition may also contain fillers. Contemplated fillers include glass beads, especially solid or hollow, traditional mineral fillers such as kaolin, magnesium, slag, carbon black, expanded or non-expanded graphite, wollastonite, nucleating agents such as silica, alumina, clay or talc, especially talc, pigments such as titanium oxide and zinc sulfide, antistatic fillers, flame retardant fillers, especially halogen-free flame retardants as described in US 2008 / 0274355, especially phosphorus-based flame retardants, for example metal salts selected from metal salts of phosphinic acid, especially dialkylphosphinates, especially aluminum diethylphosphinate or aluminum diethylphosphinate, metal salts of diphosphinic acid, mixtures of aluminum phosphinate flame retardants with nitrogen synergists or phosphinic acid salts. Examples of suitable flame retardant fillers include mixtures of aluminum phosphate flame retardants with phosphorus synergists, polymers containing at least one metal salt of phosphinic acid, especially ammonium-based ones such as ammonium polyphosphate, ammonium sulfamate, or ammonium pentaborate, or melamine-based ones such as melamine, melamine salts, melamine pyrophosphate, and melamine cyanurate, or cyanuric acid-based ones, or polymers containing at least one metal salt of diphosphonic acid or red phosphorus, antimony oxide, zinc oxide, iron oxide, magnesium oxide, or metal borates such as zinc borate, or phosphazenes, phosphams, or phosphoxynitrides, or mixtures thereof. The flame-retardant filler may also be a halogenated flame retardant such as brominated or polybrominated polystyrene, brominated polycarbonate, or brominated phenols.

[0111] Glass beads are understood to not be reinforcing fibers.

[0112] The composition may also include a flow agent.

[0113] The term "flow regulator" specifically includes prepolymers.

[0114] The prepolymer may be selected from linear or branched aliphatic, cycloaliphatic, semi-aromatic, or aromatic polyamide oligomers. The prepolymer may also be a copolyamide oligomer or a mixture of polyamide and copolyamide oligomers. Preferably, the prepolymer has a number-average molecular weight Mn of 1,000 to 10,000 g / mol, especially 1,000 to 5,000 g / mol. In particular, if the chain limiter used is, for example, a monoamine, the prepolymer may be monofunctional NH2. The number-average molecular weight (Mn) or amine number is calculated by the following formula: Mn = 1,000 / [NH2], where [NH2] is the concentration of amine functional groups in the copolyamide, determined, for example, by potentiometry.

[0115] According to one particular embodiment, the content of fluidizer relative to the total weight of the composition may vary from 0 to 10% by weight, in particular from 1 to 10% by weight, and more particularly from 5 to 10%.

[0116] According to one embodiment, the composition comprises from 1 to 5% by weight, in particular from 1 to 4% by weight, of a flow agent relative to the total weight of the composition.

[0117] According to another embodiment, the content of the flow agent relative to the total weight of the composition is 1-2% by weight; or 2-3% by weight; or 3-4% by weight; or 4-5% by weight.

[0118] The term "additives" means dyes, stabilizers, surfactants, brighteners, antioxidants, lubricants, waxes, and mixtures thereof.

[0119] The stabilizer may be an organic stabilizer or a mineral stabilizer. Typical stabilizers used with polymers include phenols, phosphites, UV absorbers, HALS (hindered amine light stabilizers) stabilizers, and metal iodides. Examples include Irganox® 1010, 245, 1098 manufactured by BASF, Irgafos® 168, 126 manufactured by BASF, Tinuvin® 312, 770 manufactured by BASF, Iodide P201 manufactured by Ciba, and Nylostab® S-EED manufactured by Clariant.

[0120] The lubricant may contain a stearate or wax binder.

[0121] The wax may in particular be an amorphous wax, such as beeswax, silicone wax, polyethylene wax, oxidized polyethylene wax, ethylene copolymer, montan wax, and polyether wax.

[0122] Several different additives of the same or different categories may be present in the composition.

[0123] The content of the additives is 0 to less than 2% by weight based on the total weight of the composition.

[0124] According to one embodiment, the composition comprises from 0.1 to less than 2% by weight, in particular from 0.5 to less than 2% by weight, of additives relative to the total weight of the composition.

[0125] According to some embodiments, the additive content in the composition may vary from 0 to 0.5% by weight; or from 0.1 to 0.5% by weight; or from 0.5 to 1% by weight; or from 1 to 1.5% by weight; or from 1.5 to less than 2% by weight.

[0126] According to a second aspect, the present invention provides a method for producing a medicament for the treatment of a pulmonary arthritis, comprising: - 25 to 65% by weight, in particular 35 to 65% by weight, of a mixture of at least one semicrystalline aliphatic polyamide and at least one amorphous polyamide, as defined above; - 35 to 75% by weight, in particular 35 to 65% by weight, of reinforcing fibers, - 0 to 10% by weight of at least one impact modifier, - 0 to 30% by weight of at least one filler, and - 0 to 10% by weight of at least one superplasticizer, and - 0 to less than 2% by weight, preferably 0.1 to less than 2% by weight, in particular 0.5 to less than 2% by weight, of additives The present invention relates to a composition, particularly a composition useful for injection molding, comprising:

[0127] All the properties defined above for the use of the mixture to prepare a composition are valid for the composition as well.

[0128] The reinforcing fibers, impact modifiers, fillers, flow agents, and additives are as previously defined herein, and all concentration ranges for the impact modifiers, flow agents, fillers, and additives previously defined herein are also valid for the composition.

[0129] Advantageously, the composition, particularly the composition useful for injection molding, comprises: - 25 to 65% by weight, in particular 35 to 65% by weight, of a mixture of at least one semicrystalline aliphatic polyamide and at least one amorphous polyamide, as defined above; - 35 to 75% by weight, in particular 35 to 65% by weight, of reinforcing fibers, - 0 to 10% by weight of at least one impact modifier, - 0 to 30% by weight of at least one filler, and - 0 to 10% by weight of at least one superplasticizer, and - 0 to less than 2% by weight, preferably 0.1 to less than 2% by weight, in particular 0.5 to less than 2% by weight, of additives The sum of the proportions of each component of the composition is equal to 100%.

[0130] Advantageously, the composition, particularly the composition useful for injection molding, comprises: - 25 to 64.9% by weight, in particular 35 to 64.9% by weight, of a mixture of at least one semicrystalline aliphatic polyamide and at least one amorphous polyamide, as defined above; - 35 to 75% by weight, in particular 35 to 65% by weight, of reinforcing fibers, - 0 to 10% by weight of at least one impact modifier, - 0 to 30% by weight of at least one filler, and - 0 to 10% by weight of at least one superplasticizer, and - 0.1 to less than 2% by weight of additives It consists of The sum of the percentages of each component of the composition equals 100%.

[0131] Advantageously, the composition, particularly the composition useful for injection molding, comprises: - 25 to 64.5% by weight, in particular 35 to 64.5% by weight, of a mixture of at least one semicrystalline aliphatic polyamide and at least one amorphous polyamide, as defined above, - 35 to 75% by weight, in particular 35 to 65% by weight, of reinforcing fibers, - 0 to 10% by weight of at least one impact modifier, - 0 to 30% by weight of at least one filler, - 0 to 10% by weight of at least one superplasticizer, and - 0.5 to less than 2% by weight of additives The sum of the proportions of each component of the composition is equal to 100%.

[0132] Advantageously, the composition, particularly the composition useful for injection molding, comprises: - 25 to 63.9% by weight, in particular 35 to 63.9% by weight, of a mixture of at least one semicrystalline aliphatic polyamide and at least one amorphous polyamide, as defined above, - 35 to 75% by weight, in particular 35 to 65% by weight, of reinforcing fibers, - 1 to 10% by weight of at least one impact modifier, - 0 to 30% by weight of at least one filler, - 0 to 10% by weight of at least one superplasticizer, and - 0.1 to less than 2% by weight of additives The sum of the proportions of each component of the composition is equal to 100%.

[0133] Advantageously, the composition, particularly the composition useful for injection molding, comprises: - 25 to 63.5% by weight, in particular 35 to 63.5% by weight, of a mixture of at least one semicrystalline aliphatic polyamide and at least one amorphous polyamide, as defined above, - 35 to 75% by weight, in particular 35 to 65% by weight, of reinforcing fibers, - 1 to 10% by weight of at least one impact modifier, - 0 to 30% by weight of at least one filler, - 0 to 10% by weight of at least one superplasticizer, and - 0.5 to less than 2% by weight of additives The sum of the proportions of each component of the composition is equal to 100%.

[0134] Advantageously, the composition, particularly the composition useful for injection molding, comprises: - 25 to 63.9% by weight, in particular 35 to 63.9% by weight, of a mixture of at least one semicrystalline aliphatic polyamide and at least one amorphous polyamide, as defined above, - 35 to 75% by weight, in particular 35 to 65% by weight, of reinforcing fibers, - 0 to 10% by weight of at least one impact modifier, - 1 to 30% by weight of at least one filler, - 0 to 10% by weight of at least one superplasticizer, and - 0.1 to less than 2% by weight of additives The sum of the proportions of each component of the composition is equal to 100%.

[0135] Advantageously, the composition, particularly the composition useful for injection molding, comprises: - 25 to 63.5% by weight, in particular 35 to 63.5% by weight, of a mixture of at least one semicrystalline aliphatic polyamide and at least one amorphous polyamide, as defined above, - 35 to 75% by weight, in particular 35 to 65% by weight, of reinforcing fibers, - 0 to 10% by weight of at least one impact modifier, - 1 to 30% by weight of at least one filler, - 0 to 10% by weight of at least one superplasticizer, and - 0.5 to less than 2% by weight of additives The sum of the proportions of each component of the composition is equal to 100%.

[0136] Advantageously, the composition, particularly the composition useful for injection molding, comprises: - 25 to 63.9% by weight, in particular 35 to 63.9% by weight, of a mixture of at least one semicrystalline aliphatic polyamide and at least one amorphous polyamide, as defined above, - 35 to 75% by weight, in particular 35 to 65% by weight, of reinforcing fibers, - 0 to 10% by weight of at least one impact modifier, - 0 to 30% by weight of at least one filler, - 1 to 10% by weight of at least one superplasticizer, and - 0.1 to less than 2% by weight of additives The sum of the proportions of each component of the composition is equal to 100%.

[0137] Advantageously, the composition, particularly the composition useful for injection molding, comprises: - 25 to 63.5% by weight, in particular 35 to 63.5% by weight, of a mixture of at least one semicrystalline aliphatic polyamide and at least one amorphous polyamide, as defined above, - 35 to 75% by weight, in particular 35 to 65% by weight, of reinforcing fibers, - 0 to 10% by weight of at least one impact modifier, - 0 to 30% by weight of at least one filler, - 1 to 10% by weight of at least one superplasticizer, and - 0.5 to less than 2% by weight of additives The sum of the proportions of each component of the composition is equal to 100%.

[0138] Advantageously, the composition, particularly the composition useful for injection molding, comprises: - 25 to 62.9% by weight, in particular 35 to 62.9% by weight, of a mixture of at least one semicrystalline aliphatic polyamide and at least one amorphous polyamide, as defined above; - 35 to 75% by weight, in particular 35 to 65% by weight, of reinforcing fibers, - 1 to 10% by weight of at least one impact modifier, - 0 to 30% by weight of at least one filler, - 1 to 10% by weight of at least one superplasticizer, and - 0.1 to less than 2% by weight of additives The sum of the proportions of each component of the composition is equal to 100%.

[0139] Advantageously, the composition, particularly the composition useful for injection molding, comprises: - 25 to 62.5% by weight, in particular 35 to 62.5% by weight, of a mixture of at least one semicrystalline aliphatic polyamide and at least one amorphous polyamide, as defined above; - 35 to 75% by weight, in particular 35 to 65% by weight, of reinforcing fibers, - 1 to 10% by weight of at least one impact modifier, - 0 to 30% by weight of at least one filler, - 1 to 10% by weight of at least one superplasticizer, and - 0.5 to less than 2% by weight of additives The sum of the proportions of each component of the composition is equal to 100%.

[0140] Advantageously, the composition, particularly the composition useful for injection molding, comprises: - 25 to 62.9% by weight, in particular 35 to 62.9% by weight, of a mixture of at least one semicrystalline aliphatic polyamide and at least one amorphous polyamide, as defined above; - 35 to 75% by weight, in particular 35 to 65% by weight, of reinforcing fibers, - 0 to 10% by weight of at least one impact modifier, - 1 to 30% by weight of at least one filler, - 1 to 10% by weight of at least one superplasticizer, and - 0.1 to less than 2% by weight of additives The sum of the proportions of each component of the composition is equal to 100%.

[0141] Advantageously, the proportion of filler in the latter composition is between 5 and 30% by weight, in particular between 10 and 30% by weight and preferentially between 15 and 30% by weight, the maximum amount of mixture of semicrystalline and amorphous polyamide present then being 58.9%; 53.9% and 48.9% respectively.

[0142] Advantageously, the composition, particularly the composition useful for injection molding, comprises: - 25 to 62.5% by weight, in particular 35 to 62.5% by weight, of a mixture of at least one semicrystalline aliphatic polyamide and at least one amorphous polyamide, as defined above; - 35 to 75% by weight, in particular 35 to 65% by weight, of reinforcing fibers, - 0 to 10% by weight of at least one impact modifier, - 1 to 30% by weight of at least one filler, - 1 to 10% by weight of at least one superplasticizer, and - 0.5 to less than 2% by weight of additives The sum of the proportions of each component of the composition is equal to 100%.

[0143] Advantageously, the proportion of filler in the latter composition is between 5 and 30% by weight, in particular between 10 and 30% by weight and preferentially between 15 and 30% by weight, the maximum amount of mixture of semicrystalline and amorphous polyamide present then being 58.5%; 53.5% and 48.5% respectively.

[0144] Advantageously, the composition, particularly the composition useful for injection molding, comprises: - 25 to 61.9% by weight, in particular 35 to 61.9% by weight, of a mixture of at least one semicrystalline aliphatic polyamide and at least one amorphous polyamide, as defined above, - 35 to 75% by weight, in particular 35 to 65% by weight, of reinforcing fibers, - 1 to 10% by weight of at least one impact modifier, - 1 to 30% by weight of at least one filler, - 1 to 10% by weight of at least one superplasticizer, and - 0.1 to less than 2% by weight of additives The sum of the proportions of each component of the composition is equal to 100%.

[0145] Advantageously, the proportion of filler in the latter composition is between 5 and 30% by weight, in particular between 10 and 30% by weight and preferentially between 15 and 30% by weight, the maximum amount of mixture of semicrystalline and amorphous polyamide present then being 57.9%; 52.9% and 47.9% respectively.

[0146] Advantageously, the composition, particularly the composition useful for injection molding, comprises: - 25 to 61.5% by weight, in particular 35 to 61.5% by weight, of a mixture of at least one semicrystalline aliphatic polyamide and at least one amorphous polyamide, as defined above; - 35 to 75% by weight, in particular 35 to 65% by weight, of reinforcing fibers, - 1 to 10% by weight of at least one impact modifier, - 1 to 30% by weight of at least one filler, - 1 to 10% by weight of at least one superplasticizer, and - 0.5 to less than 2% by weight of additives The sum of the proportions of each component of the composition is equal to 100%.

[0147] Advantageously, the proportion of filler in the latter composition is between 5 and 30% by weight, in particular between 10 and 30% by weight and preferentially between 15 and 30% by weight, the maximum amount of mixture of semicrystalline and amorphous polyamide present then being 57.5%; 52.5% and 47.5% respectively.

[0148] In one embodiment, the proportion of fillers in the composition of the invention is 0 to 28% by weight, in particular 1 to 28% by weight, 5 to 28% by weight, in particular 10 to 28% by weight and preferentially 15 to 28% by weight.

[0149] According to a third aspect, the present invention relates to a process for the manufacture of a composition as defined hereinbefore, in which the components of said composition are mixed by compounding, in particular in a twin-screw extruder, preferably a co-rotating extruder, a co-mixer or an internal mixer.

[0150] Finally, according to a fourth aspect, the present invention relates to a molded article obtainable from a composition as defined hereinbefore by injection molding.

[0151] Advantageously, the shaped article is for electrical and electronic applications, in particular for applications selected from the group consisting of televisions, digital cameras, digital games, telephone parts, digital tablets, drones, printers, or computer parts.

[0152] In another embodiment, the molded article is a sports article, in particular a ski boot or ski boot part, or a rigid shoe with cleats, such as soccer, rugby or football cleats, hockey footwear or parts of hockey footwear, or a running shoe, a golf ball or parts of a golf ball, or a lacrosse stick, or even a hockey article such as a helmet, or a sports article for protecting the head, shoulders, elbows, hands, knees, back or shins, such as a helmet, glove, shoulder pads, elbow pads, knee pads or shin guards. [Example]

[0153] The present invention will be described in more detail in the following examples.

[0154] Example 1 Synthesis of the (co)polyamides of the present invention The various polyamides and copolyamides of the present invention were prepared by conventional techniques for polyamide and copolyamide synthesis.

[0155] Synthesis of PA B10, a representative of various homopolyamides: The monomer bis-(3-methyl-4-aminocyclohexyl)-methane (B) and sebacic acid are charged together into the reactor. The medium is first inerted to remove oxygen, which can cause yellowing or secondary reactions. Water can also be charged to improve heat exchange and promote the melting of the monomers. Two temperature increases and pressure plateaus are carried out. The temperature (T°) and pressure conditions are selected to melt the medium. After reaching the maintenance conditions, degassing is carried out and the polycondensation reaction takes place. The medium gradually becomes viscous, and the reaction water that forms is entrained by applying a nitrogen purge or vacuum. Once the stop condition for the desired viscosity is reached, stirring is stopped and extrusion and granulation can begin. The resulting granules are then compounded with glass fibers.

[0156] Synthesis of PA 11 / B10, a representative of various copolyamides: The monomers aminoundecanoic acid, bis-(3-methyl-4-aminocyclohexyl)-methane (B), and sebacic acid are charged together in the reactor according to the desired mass ratio. The medium is first inerted to remove oxygen, which can cause yellowing or secondary reactions. Water can also be added to improve heat exchange and promote the melting of the monomers. Two temperature increases and pressure plateaus are carried out. The temperature (T°) and pressure conditions are selected to melt the medium. After reaching the maintenance conditions, degassing is carried out and the polycondensation reaction takes place. The medium gradually becomes viscous, and the reaction water that forms is entrained by applying a nitrogen purge or vacuum. Once the stop condition for the desired viscosity is reached, stirring is stopped and extrusion and granulation can begin. The resulting granules are then blended with glass fibers.

[0157] combination The compositions were prepared by mixing the polymer granules with short fibers when melted. The mixing was carried out by compounding in a co-rotating twin-screw extruder with a screw diameter of 26 mm, with a flat temperature profile (T°) at 290°C for compositions CE1 to CE3 and 11 to 18, and at 230°C for compositions 19, 110 and CE4. The screw speed was 250 rpm and the flow rate was 20 kg / h.

[0158] The introduction of the glass fibers is achieved by side feeding.

[0159] The (co)polyamide, fibers, additives and possibly fillers are added during the compounding process in the main hopper for compositions CE1-CE3 and 11-18.

[0160] For compositions 18 and 19 and CE4, the resin and additives are introduced into the main hopper, the addition of the filler is made by means of the first side gutter and the addition of the glass fibre in the second side gutter.

[0161] The following compositions were prepared (E=inventive examples, CE=comparative examples, values ​​correspond to percentages by weight): TIFF2025179072000001.tif98170TIFF2025179072000002.tif86170Values ​​are weight percentages.

[0162] BMNO: Rilsan® BMNO sold by Arkema

[0163] Flame retardant: OP1312 (Clariant)

[0164] CSX3J-451 circular cross-section fiber, sold by Nittobo Injection

[0165] 100×100×1mm 3 Plates were prepared by injecting different compositions - Injection temperature: 260℃ - Mold temperature: 80℃

[0166] The cycle time is adjusted depending on the composition to allow for ejection of the composition and is less than 50 seconds.

[0167] Compositions 11-110 all have a Tg that is more than 5° C. greater than that of comparative compositions CE1-CE3.

[0168] The polyamide blends of compositions 11 to 18 in Table 1 and 19 to 110 in Table 2 all have crystallization enthalpies greater than 30 J / g.

[0169] Example 2 Change in flexural modulus with temperature and humidity To evaluate the effect of humidity and temperature on the flexural modulus, the flexural modulus of specimens of the resulting compositions was measured in an Instron 5966 machine manufactured by Instron, Inc. The compositions were dry compositions and compositions previously saturated in water at 65°C.

[0170] The tests were carried out at different temperatures ranging from -10°C to 60°C.

[0171] Specimens were cut from the injection-molded plates in the direction of injection, with dimensions according to ISO 178 except for a thickness of 1 mm.

[0172] The results are shown in Tables 3-4 below. TIFF2025179072000003.tif66170TIFF2025179072000004.tif28170

[0173] Table 4 shows that the compositions of the present invention have higher flexural modulus stability than the comparative compositions CE1 and CE4.

[0174] Example 3 Change in tensile modulus with temperature and humidity To evaluate the effect of humidity and temperature on the tensile modulus, the tensile modulus of specimens of the resulting compositions was measured in an Instron 5966 machine manufactured by Instron, Inc. The compositions were dry compositions and compositions previously saturated in water at 65°C.

[0175] The tests were carried out at different temperatures ranging from -10°C to 60°C.

[0176] Specimens were cut from the injection-molded plates in the direction of injection, with dimensions according to ISO 527 except for a thickness of 1 mm.

[0177] The same trend observed for the flexural modulus is found for the tensile modulus.

Claims

1. 1. Use of a mixture of at least one semicrystalline aliphatic polyamide and at least one amorphous polyamide for preparing a semicrystalline composition having a tensile modulus or flexural modulus that does not vary by more than 25% in the temperature range of 10°C to 40°C, particularly in the temperature range of 0°C to 40°C, and especially in the temperature range of -10°C to 40°C, wherein the at least one semicrystalline aliphatic polyamide is At least one type of C ６ ~C １８ , with priority given to C １０ ~C １８ , more preferentially C １０ ~C １２ amino acids, or At least one type of C ６ ~C １８ , with priority given to C １０ ~C １８ , more preferentially C １０ ~C １２ lactam, or At least one type of C ４ ~C ３６ , with priority given to C ５ ~C １８ , with priority given to C ５ ~C １２ , more preferentially C １０ ~C １２ and at least one aliphatic diamine Ca of C ４ ~C ３６ , with priority given to C ６ ~C １８ , with priority given to C ６ ~C １２ , more preferentially C １０ ~C １２ and an aliphatic dicarboxylic acid Cb of Use obtained by polycondensation of

2. 2. The use according to claim 1, wherein the modulus of elasticity does not vary by more than 35% in the temperature range from -10°C to 50°C.

3. 3. Use according to claim 1 or 2, in which the Tg of the semi-crystalline composition, determined by DMA according to ISO 6721-11:2019, shows an increase of at least 5°C, preferentially at least 10°C, more preferentially at least 15°C, relative to the initial Tg of the semi-crystalline polyamide before mixing.

4. The at least one amorphous polyamide is a homopolyamide of formula XY or a copolyamide of formula A / XY, wherein XY is a mixture of at least one cycloaliphatic diamine (X) and at least one C ４ ~C ３６ , with priority given to C ６ ~C １８ , with priority given to C ６ ~C １２ , more preferentially C １０ ~C １２ A is a repeating unit obtained by polycondensation with an aliphatic dicarboxylic acid (Y) or at least one aromatic dicarboxylic acid (Y), ６ ~C １８ , with priority given to C １０ ~C １８ , more preferentially C １０ ~C １２ amino acids, or At least one type of C ６ ~C １８ , with priority given to C １０ ~C １８ , more preferentially C １０ ~C １２ lactam, or At least one type of C ４ ~C ３６ , with priority given to C ５ ~C １８ , with priority given to C ５ ~C １２ , more preferentially C １０ ~C １２ and at least one Ca diamine of C ４ ~C ３６ , with priority given to C ６ ~C １８ , with priority given to C ６ ~C １２ , more preferentially C １０ ~C １２ and dicarboxylic acid Cb The use according to any one of claims 1 to 3, wherein the repeating unit is obtained by polycondensation of

5. 5. Use according to claim 4, wherein the at least one amorphous polyamide is a copolyamide of formula A / XY, wherein A is obtained by polycondensation of at least one amino acid or by polycondensation of at least one lactam, X is selected from bis-(3-methyl-4-aminocyclohexyl)-methane (B) or bis(p-aminocyclohexyl)-methane (P) or bis(aminomethyl)cyclohexane (BAC), and Y is terephthalic acid and / or isophthalic acid.

6. 6. Use according to claim 4 or 5, wherein A / XY is selected from the units 11 / BI / BT, 12 / BI / BT, 11 / BACI / BACT, 12 / BACI / BACT, 11 / BACI, 12 / BACI, 11 / PI / PT, 12 / PI / PT, and mixtures thereof.

7. 5. Use according to claim 4, wherein the at least one amorphous polyamide is a copolyamide of formula A / XY, wherein A is obtained by polycondensation of at least one amino acid or by polycondensation of at least one lactam, X is selected from bis-(3-methyl-4-aminocyclohexyl)-methane (B) or bis(p-aminocyclohexyl)-methane (P), and Y is sebacic acid or dodecanedioic acid.

8. 8. Use according to claim 4 or 7, wherein A / XY is selected from the units 11 / B10, 11 / B12, 11 / P10, 11 / P12, 12 / B10, 12 / B12, 12 / P10, 12 / P12, and mixtures thereof.

9. 5. Use according to claim 4, wherein the at least one amorphous polyamide is a copolyamide of formula A / XY, wherein A is obtained by polycondensation of at least one diamine Ca with at least one dicarboxylic acid Cb, X is selected from bis-(3-methyl-4-aminocyclohexyl)-methane (B) or bis(p-aminocyclohexyl)-methane (P), and Y is sebacic acid or dodecanedioic acid.

10. 10. Use according to claim 4 or 9, wherein A / XY is selected from the units 1010 / B10, 1010 / B12, 1010 / P10, 1010 / P12, 1012 / B10, 1012 / B12, 1012 / P10, 1012 / P12, 1210 / B10, 1210 / B12, 1210 / P10, 1210 / P12, 1212 / B10, 1212 / B12, 1212 / P10, 1212 / P12, and mixtures thereof.

11. 5. The use according to claim 4, wherein the at least one amorphous polyamide is a homopolyamide of formula XY, where X is selected from bis-(3-methyl-4-aminocyclohexyl)-methane (B) or bis(p-aminocyclohexyl)-methane (P), and Y is sebacic acid or dodecanedioic acid.

12. 12. Use according to claim 4 or 11, wherein XY is selected from units B10, B12, P10, P12, and mixtures thereof.

13. 13. Use according to any one of claims 1 to 12, wherein the semi-crystalline copolyamide has a crystallization enthalpy of more than 30 J / g.

14. Use according to any one of claims 1 to 13, in which the proportion by weight of the amorphous polyamide is between 10 and 45%, preferentially between 15 and 35% by weight and more preferentially between 20 and 30% by weight relative to the sum by weight of the at least one semi-crystalline polyamide and the at least one amorphous polyamide.

15. Use according to any one of claims 1 to 14, wherein the composition comprises 35 to 75% by weight of reinforcing fibres, in particular 35 to 65% by weight of reinforcing fibres.

16. 16. Use according to claim 15, wherein the reinforcing fibres are selected from glass fibres and carbon fibres or mixtures thereof, in particular glass fibres.

17. 17. Use according to claim 16, wherein the glass fibres are selected from glass fibres with a non-circular cross section and glass fibres with a circular cross section, carbon fibres and mixtures thereof, in particular glass fibres with a non-circular cross section and glass fibres with a circular cross section and mixtures thereof, in particular glass fibres with a circular cross section.

18. - 25 to 65% by weight, in particular 35 to 65% by weight, of a mixture of at least one semicrystalline aliphatic polyamide and at least one amorphous polyamide according to any one of claims 1 to 14, - 35 to 75% by weight, in particular 35 to 65% by weight, of reinforcing fibers, - 0 to 10% by weight of at least one impact modifier, - 0 to 30% by weight of at least one filler, and - 0 to 10% by weight of at least one superplasticizer, and - 0 to less than 2% by weight, preferably 0.1 to less than 2% by weight, in particular 0.5 to less than 2% by weight of additives 1. A composition, particularly a composition useful for injection molding, comprising:

19. 20. A method for producing a composition according to claim 18, wherein the components of said composition are mixed by compounding, in particular in a twin-screw extruder, a co-mixer or an internal mixer.

20. 19. A molded article obtainable by injection molding from the composition according to claim 18.

21. 21. The molded article of claim 20 for electrical and electronic applications, in particular for applications selected from the group consisting of televisions, digital cameras, digital games, phone parts, digital tablets, drones, printers, or computer parts.

22. 21. A shaped article according to claim 20 for sports applications, in particular ski boots or ski boot parts, or rigid shoes with cleats, e.g. soccer, rugby or football footwear, hockey footwear or parts of hockey footwear, or running shoes, golf balls or parts of golf balls, or lacrosse sticks, and also hockey articles such as helmets, or sports articles for protecting the head, shoulders, elbows, hands, knees, back or shins, e.g. helmets, gloves, shoulder pads, elbow pads, knee pads or shin guards.

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