Copolyamide compositions comprising reinforcing fibers and having high modulus stability and uses thereof

Abstract

The present invention relates to the use of a copolyamide of formula A / X1Y comprising at least two different units A and X1Y for preparing a composition, wherein: -A is a repeating unit obtained by polycondensation of: at least one C9-C 18 , preferably C 10 ‑C 18 More preferably C 10 ‑C 12 Amino acids, or at least one C9‑C 18 , preferably C 10 ‑C 18 More preferably C 10 ‑C 12 lactam, or at least one C4-C 36 , preferably C6-C 18 , preferably C6-C 12 More preferably C 10 ‑C 12 Diamine Ca and at least one C4-C 36 , preferably C6-C 18 , preferably C6-C 12 More preferably C 10 ‑C 12 The dicarboxylic acid Cb;-X1Y is obtained from at least one C9-C 18 , preferably C 10 ‑C 18 More preferably C 10 ‑C 12 Repeating units of polycondensation of a linear aliphatic diamine (X1) and at least one aromatic dicarboxylic acid (Y), the composition comprising 35-65% and preferably 50-65% by weight of reinforcing fibers relative to the total weight of the composition, and for the composition, the flexural modulus or the tensile modulus measured after the same conditioning varies by no more than 20% in the temperature range of 20°C to 40°C, in particular in the temperature range of 0°C to 40°C, more particularly in the temperature range of -10°C to 40°C.

Description

Technical Field

[0001] The present patent application relates to the use of semiaromatic copolyamides for producing compositions having a high modulus stability under the influence of temperature and humidity, to a process for their production and to said compositions. Background Art

[0002] Many applications in the E / E field require the use of high modulus polymer materials, for example for televisions, digital cameras, digital game consoles, phone parts, digital tablets, drones, printers or computer parts. The modulus of the material is indeed a key factor that allows lower weight, because the modulus of the material enables the thickness of the part to be reduced while maintaining high rigidity. A distinction is made between different moduli (e.g. tensile modulus, flexural modulus, etc.). These moduli can be affected by the humidity level and temperature of the sample.

[0003] Equally important, stiffness is hardly affected by changes in the water content or temperature of the material. Indeed, modulus stability is also an important factor for subsequent use or to ensure easy assembly of the parts when such assembly is carried out where the temperature and / or humidity may be high.

[0004] It is therefore desirable to find polymers whose modulus remains stable over the temperature and / or humidity ranges to which they are exposed, especially during assembly of components and subsequent operation of the device. Preferably, the modulus is stable over a temperature range of 20°C to 40°C, especially over a temperature range of 0°C to 40°C, especially over a temperature range of -10°C to 40°C, for compositions having different water contents (resulting from conditioning the composition in an atmosphere where the humidity may be 0-100%, or in liquid water).

[0005] Furthermore, the polymer formulation must have a moderate molding temperature and crystallize rapidly enough to allow conversion times, especially cycle times, suitable for industrial processes.

[0006] However, aliphatic polyamides generally experience a significant loss of rigidity when the temperature is increased, especially when these polyamides have been previously conditioned in a humid atmosphere since they contain a certain amount of water.

[0007] It is known from application WO 2018 / 073536 that semiaromatic polyamides, in particular MXDZ polyamides, are used in blends with aliphatic polyamides, in particular semicrystalline polyamides, containing glass fibers having a circular cross section in order to limit the warpage of the resulting composition.

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

[0009] Furthermore, document WO 10 / 015785 describes a copolyamide comprising at least two different A / XT units, characterised in that the copolyamide has a content of amine chain ends greater than or equal to 20 μeq / g, a content of acid chain ends less than or equal to 100 μeq / g and a content of non-reactive chain ends greater than or equal to 20 μeq / g. The copolyamide may contain additives, in particular reinforcing fibres which may be glass fibres.

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

[0011] International application WO 2014 / 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 an elastic modulus of at least 76 GPa, determined according to ASTM C1557-03.

[0012] None of these prior art documents mentions 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 having both a high modulus and good injection mouldability, wherein the high modulus is stable over a wide temperature range, even when the composition is saturated with water. Summary of the invention

[0014] It was therefore an object of the present invention to provide semiaromatic copolyamides for the production of compositions having a high modulus stability at the temperature and humidity stiffness.

[0015] Therefore, according to a first aspect, the object of the present invention is a 1 Y contains at least two different units A and X 1 Use of a copolyamide of Y for preparing a composition, wherein:

[0016] -A is a repeating unit obtained by the polycondensation of:

[0017] At least one C 9 -C18 , preferably C 10 -C 18 More preferably C 10 -C 12 Amino acids, or

[0018] At least one C 9 -C 18 , preferably C 10 -C 18 More preferably C 10 -C 12 lactam, or

[0019] At least one C 4 -C 36 , preferably C 6 -C 18 , preferably C 6 -C 12 More preferably C 10 -C 12 diamine Ca and at least one C 4 -C 36 , preferably C 6 -C 18 , preferably C 6 -C 12 More preferably C 10 -C 12 Dicarboxylic acid Cb;

[0020] -X 1 Y is composed of at least one linear aliphatic C 9 -C 18 , preferably C 10 -C 18 More preferably C 10 -C 12 Diamine (X 1 ) and at least one aromatic dicarboxylic acid (Y),

[0021] The modulus of the composition does not vary by more than 20% in the temperature range of 20°C to 40°C, particularly in the temperature range of 0°C to 40°C, particularly in the temperature range of -10°C to 40°C.

[0022] In other words, the object of the present invention is to use the formula A / X as defined above 1 Y contains at least two different units A and X 1 The copolyamide of Y is used to prepare a composition, the modulus of which varies by no more than 20% in a temperature range of 20°C to 40°C, in particular in a temperature range of 0°C to 40°C, and in particular in a temperature range of -10°C to 40°C, compared to the variation of the modulus of the aliphatic homopolyamide measured under the same conditions.

[0023] Or in other words, the object of the present invention is to use the formula A / X as defined above 1 Y contains at least two different units A and X 1 The copolyamide of Y is used to prepare a composition, the modulus of which varies by no more than 20% in the temperature range of 20°C to 40°C, in particular in the temperature range of 0°C to 40°C, and in particular in the temperature range of -10°C to 40°C, compared to the variation of the modulus of the aliphatic homopolyamide having the same units A measured under the same conditions.

[0024] Or in other words, the object of the present invention is to use a compound comprising the formula A / X as defined above 1 Y contains at least two different units A and X 1 The invention relates to a composition of a copolyamide of Y, so as to limit the variation of the modulus in the temperature range of 20°C to 40°C, in particular in the temperature range of 0°C to 40°C, in particular in the temperature range of -10°C to 40°C, to no more than 20% compared to the variation of the modulus of said composition measured under the same conditions in which an aliphatic homopolyamide is used instead of said copolyamide.

[0025] Or in other words, the object of the present invention is to use a compound comprising the formula A / X as defined above 1 Y contains at least two different units A and X 1 A composition of a copolyamide of Y, so as to limit the variation of the modulus in the temperature range of 20°C to 40°C, in particular in the temperature range of 0°C to 40°C, in particular in the temperature range of -10°C to 40°C, to no more than 20% compared to the variation of the modulus of said composition measured under the same conditions in which an aliphatic homopolyamide having the same units A is used instead of said copolyamide.

[0026] Unexpectedly, the inventors found that the selection of a repeating unit X based on an aromatic diacid 1 The semiaromatic copolyamides of Y and repeating units A make it possible to prepare compositions whose modulus not only exhibits stability under the influence of temperature and humidity and does not vary by more than 20% in the temperature range of 20° C. to 40° C., in particular in the temperature range of 0° C. to 40° C., especially in the temperature range of −10° C. to 40° C., but whose processing is facilitated by low molding temperatures, in particular low molding temperatures below 100° C., preferably below 90° C., and by short cycle times during their processing.

[0027] The nomenclature used to define polyamides is described in ISO Standard 1874-1:2011 “Plastiques—Material aux polyamides (PA) pour moulage et extrusion—Partie 1: Designation”, in particular on page 3 (Tables 1 and 2), and is well known to those skilled in the art.

[0028] When the repeating units A of the copolyamide are obtained from the polycondensation of at least one lactam, the at least one lactam may be selected from C 9 -C 18 , preferably C 10 -C 18 More preferably C 10 -C 12 Lactam. C 10 -C 12 Lactams are in particular caprolactam, undecanolactam and laurolactam.

[0029] The units A result from the polycondensation of at least one lactam and may therefore comprise a single lactam or a plurality of lactams.

[0030] Advantageously, the units A result from the polycondensation of a single lactam and the lactam is laurolactam.

[0031] When the repeating units A of the copolyamide are obtained from the polycondensation of at least one amino acid, the at least one amino acid may be selected from C 9 -C 18 , preferably C 10 -C 18 More preferably C 10 -C 12 Amino acids.

[0032] C 9 -C 12 The amino acids are especially 9-aminononanoic acid, 10-aminodecanoic acid, 10-aminoundecanoic acid, 12-aminododecanoic acid and 11-aminoundecanoic acid and derivatives thereof, especially N-heptyl-11-aminoundecanoic acid.

[0033] The unit A is derived from the polycondensation of at least one amino acid and may therefore comprise a single amino acid or a plurality of amino acids.

[0034] Advantageously, said unit A is obtained from the polycondensation of a single amino acid and said amino acid is 11-aminoundecanoic acid.

[0035] When the repeating units A of the copolyamide are derived from at least one C 4 -C 36 , preferably C 6 -C18 , preferably C 6 -C 12 More preferably C 10 -C 12 diamine Ca and at least one C 4 -C 36 , preferably C 6 -C 18 , preferably C 6 -C 12 More preferably C 10 -C 12 In the polycondensation of the diacid Cb, the at least one diamine Ca is a linear or branched, in particular a linear aliphatic diamine, and the at least one diacid Cb is a linear or branched aliphatic, in particular a linear diacid.

[0036] Advantageously, the at least one diamine is linear aliphatic and the at least one diacid is aliphatic and linear.

[0037] The at least one C 4 -C 36 The 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-undemethylenediamine, 1,12-dodecamethylenediamine, 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,16-hexadecamethylenediamine and 1,18-octadecamethylenediamine, octadecenediamine, eicosanediamine, docosanediamine and diamines derived from fatty acids.

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

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

[0040] Advantageously, the diamine Ca used is C10 -C 12 Diamines, in particular selected from 1,10-decamethylenediamine, 1,11-undemethylenediamine and 1,12-dodecamethylenediamine.

[0041] The at least one C 4 -C 36 The dicarboxylic acid Cb may be chosen from succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, octadecenediamine, eicosanediamine, docosanediamine and diamines derived from fatty acids.

[0042] Advantageously, the at least one dicarboxylic acid Cb is C 6 -C 18 And selected from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, and octadecanedioic acid.

[0043] Advantageously, the at least one dicarboxylic acid Cb is C 6 -C 12 And selected from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid and dodecanedioic acid.

[0044] Advantageously, the at least one dicarboxylic acid Cb is C 10 -C 12 and is selected from the group consisting of sebacic acid, undecanedioic acid and dodecanedioic acid.

[0045] The units A result from the polycondensation of at least one diamine Ca and at least one dicarboxylic acid Cb and may therefore comprise a single diamine or a plurality of diamines and a single dicarboxylic acid or a plurality of dicarboxylic acids.

[0046] Advantageously, the units A result from the polycondensation of a single diamine Ca with a single dicarboxylic acid Cb.

[0047] The unit X 1 Y is derived from at least one C 9 -C 18 , preferably C 10 -C 18 More preferably C 10 -C 12 Linear aliphatic diamine (X 1 ) and at least one aromatic dicarboxylic acid (Y) are condensation-polymerized repeating units.

[0048] The linear aliphatic diamine (X 1 ) is as defined for the linear aliphatic diamine Ca.

[0049] The linear aliphatic diamine (X1 ) may be identical to or different from the linear and aliphatic diamine Ca.

[0050] The aromatic dicarboxylic acid (Y) may be C 6 -C 18 , C 6 -C 18 , preferably C 8 -C 18 More preferably C 8 -C 12 .

[0051] Advantageously, it is chosen from terephthalic acid (T), isophthalic acid (I) or naphthalene dicarboxylic acid (N).

[0052] In an advantageous embodiment, the aromatic dicarboxylic acid (Y) is terephthalic acid.

[0053] The modulus of a composition varies based on temperature, and typically, the modulus decreases as temperature increases.

[0054] The expression "modulus does not vary by more than 20% in the temperature range of 20°C to 40°C" means that in this temperature range of 20°C to 40°C, the modulus of the same composition (whether it is the flexural modulus or the tensile modulus measured after the same conditioning (dry or wet atmosphere)) does not vary by more than 20%.

[0055] The term "wet conditioned" means after saturation in liquid water at 65°C.

[0056] Of course, the same applies to other temperature ranges.

[0057] In other words, for a composition conditioned under the same dry or wet atmosphere conditions, M 20 M is the modulus measured at 20°C T is the modulus measured at temperature T, then:

[0058] ((M 20 –M T ) / M 20 )x 100≤20, wherein T is 20 to 40°C.

[0059] Advantageously, for a composition conditioned under the same dry or wet atmospheric conditions, the modulus does not vary by more than 20% over the temperature range of 0°C to 40°C, so that ((M 0 –M T ) / M 0 )x 100≤20, wherein T is 0 to 40°C.

[0060] More advantageously, for a composition conditioned under the same dry or wet atmospheric conditions, the modulus does not vary by more than 20% over the temperature range of -10°C to 40°C, so that ((M -10 –M T ) / M -10 )x 100≤20, wherein T is -10 to 40°C.

[0061] Advantageously, for a composition conditioned under the same humid atmosphere conditions, the modulus does not vary by more than 15% over the temperature range of 0°C to 40°C, so that ((M 0 –M T ) / M 0 )x 100≤15, wherein T is 0 to 40°C.

[0062] More advantageously, for a composition conditioned under the same humid atmosphere conditions, the modulus does not vary by more than 15% over the temperature range of -10°C to 40°C, so that ((M -10 –M T ) / M -10 )x 100≤15, where T is -10 to 40°C.

[0063] Advantageously, for a composition conditioned under the same dry atmosphere conditions, the modulus does not vary by more than 5% over the temperature range of 0°C to 40°C, so that ((M 0 –M T ) / M 0 )x 100≤5, wherein T is 0 to 40°C.

[0064] More advantageously, for a composition conditioned under the same dry atmosphere conditions, the modulus does not vary by more than 5% over the temperature range of -10°C to 40°C, so that ((M -10 –M T ) / M -10 )x 100≤5, where T is -10 to 40°C.

[0065] In one embodiment, the modulus is measured according to ISO 178:2010 as defined above and corresponds to the flexural modulus.

[0066] In another embodiment, the modulus is measured according to ISO 527-1 and 2:2012 and corresponds to the tensile modulus as defined above.

[0067] In another embodiment, the modulus corresponds to both flexural modulus and tensile modulus, both measured as defined above.

[0068] Advantageously, the ratio of the flexural modulus measured at 20°C on a sample saturated in water at 65°C to the flexural modulus measured at 20°C on a dry sample is lower than 10%, in particular lower than 7%, both measurements being carried out according to ISO 178:2010.

[0069] In one embodiment, the X of the copolyamide defined above 1 The Y unit is composed of at least one C 10 -C 18 More preferably C 10 -C 12 Aliphatic diamine (X 1 ) and at least one aromatic dicarboxylic acid (Y) by condensation polymerization.

[0070] X 1 Examples of Y units are 10I, 10T, 10N, 12I, 12T, 12N, 14I, 14T, 14N.

[0071] Advantageously, the copolyamide has the formula A / X 1 T.

[0072] Advantageously, the X of the copolyamide defined above is 1 The Y unit is composed of at least one C 10 -C 12 Aliphatic diamine (X 1 ) and at least one aromatic dicarboxylic acid (Y) by condensation polymerization.

[0073] X 1 Examples of Y units are 10I, 10T, 10N, 12I, 12T, 12N.

[0074] Advantageously, X 1 The Y unit is selected from 10T and 12T.

[0075] Advantageously, the copolyamide has the formula A / 10T or A / 12T, preferably A / 10T.

[0076] In another embodiment, the unit A of the copolyamide as defined above is an amino acid or a lactam as defined above.

[0077] Advantageously, the copolyamide has the formula A / X 1 Y, wherein A is an amino acid or a lactam as defined above, and X 1 Y is as defined above.

[0078] Advantageously, the copolyamide has the formula A / X 1 T, wherein A is an amino acid or a lactam as defined above.

[0079] Advantageously, the copolyamide has the formula A / 10T or A / 12T, preferably A / 10T, wherein A is an amino acid or a lactam as defined above.

[0080] In another embodiment, the units A of the copolyamide defined above are respectively 11 or C 12 Amino acids or lactams.

[0081] Advantageously, the copolyamide has the formula A / X 1 Y, where A is C 11 or C 12 Amino acid or lactam and X 1 Y is as defined above.

[0082] In yet another embodiment, said copolyamide as defined above is semi-crystalline.

[0083] In the meaning of the present invention, a semicrystalline copolyamide is a copolyamide having a melting temperature (Tm) obtained by DSC according to ISO Standard 11357-3:2013 and a crystallization enthalpy during a cooling step carried out at a rate of 20 K / min, measured by DSC according to ISO Standard 11357-3, 2013, of higher than 30 J / g, preferably higher than 35 J / g.

[0084] Advantageously, the copolyamide has a Tm of ≤280°C, in particular ≤270°C, especially ≤265°C.

[0085] Therefore, in this embodiment, the A and X in the copolyamide of the present invention are adjusted based on different units. 1 The molar ratio of Y units is such that the copolyamide is semi-crystalline.

[0086] In another embodiment, the formula A / X 1 The copolyamide of Y consists only of A and X as defined above 1 Y unit composition.

[0087] Thus, in this embodiment, the copolyamide has only one or more A units and only one or more X 1 Y unit; however, A is a repeating unit derived from the polycondensation of at least one amino acid or at least one lactam or at least one Ca diamine with at least one Cb dicarboxylic acid as defined above, and X 1 Y is derived from at least one linear aliphatic diamine (X 1 ) and at least one aromatic dicarboxylic acid (Y) as defined above.

[0088] In another embodiment, the formula A / X 1 The copolyamide Y consists of only one A unit as defined above and one X 1 Y unit composition.

[0089] Thus, in this embodiment, the copolyamide has only one A unit and only one X 1 Y unit, and A is a repeating unit derived from the polycondensation of an amino acid or a lactam or a Ca diamine with a Cb dicarboxylic acid as defined above, and X 1 Y is derived from a linear aliphatic diamine (X 1 ) and an aromatic dicarboxylic acid (Y) as defined above.

[0090] Advantageously, the copolyamide is selected from PA11 / 10T, PA11 / 12T, PA12 / 10T, PA12 / 12T, PA610 / 10T, PA610 / 12T, PA612 / 10T, PA612 / 12T, PA1010 / 10T, PA1012 / 10T, PA1010 / 12T, PA1012 / 12T, PA1210 / 10T, PA1212 / 10T, PA1210 / 12T, PA1212 / 12T, in particular PA11 / 10T

[0091] In another embodiment, the copolyamide comprises at least one 1 The Y unit is different from the third Z unit and has the general formula A / X 1 Y / Z

[0092] in:

[0093] A and X 1 The Y unit is as defined above,

[0094] Z is selected from units derived from amino acids, units derived from lactams and units of formula (Cc diamine).(Cd diacid) wherein c represents the number of carbon atoms in the diamine and d represents the number of carbon atoms in the diacid, c and d are each 4 to 36 and advantageously 9 to 18, inclusive,

[0095] Provided that caprolactam or aminocaproic acid are excluded from the definition of lactam and amino acid of Z and when the Cc diamine is a C6 diamine, then terephthalic acid is excluded from the definition of Cd diacid.

[0096] It is very clear that when the formula A / X 1 The copolyamide of Y consists only of units A and X as defined above 1 When Y is composed, or when the formula A / X 1 The copolyamide of Y consists only of one unit A and one unit X as defined above.1 When Y is used as the component, the third Z unit cannot exist.

[0097] However, in the presence of at least one 1 In this embodiment of the third Z unit with different Y, the copolyamide of the present invention may comprise one or more A units and one or more X 1 Y unit and at least one Z unit.

[0098] The term "different" means that even if there are multiple A and / or X 1 Y units and Z units, when present, also interact with A and X units present in the copolyamide. 1 The Y units are different, but the Z units can also be of the same type as A, i.e., repeating units derived from the polycondensation of lactams, or amino acids, or Ca diamines and Cb dicarboxylic acids, or from X 1 Y is of the same type, i.e., derived from at least one linear aliphatic C 9 -C 18 Diamine (X 1 ) and at least one aromatic dicarboxylic acid (Y) are condensation-polymerized repeating units.

[0099] When Z represents a unit derived from an amino acid, it 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.

[0100] When Z represents a unit derived from a lactam, the lactam may be selected from pyrrolidone, 2-piperidone, caprolactam, enantholactam, caprolactam, nonanolactam, caprolactam, undecanolactam and laurolactam.

[0101] When the Z unit is a unit of formula (Cc diamine).(Cd diacid), the unit (Cc diamine) is selected from aliphatic, linear or branched diamines, alicyclic diamines and arylaliphatic diamines.

[0102] When the diamine is aliphatic and linear, it is selected from butanediamine, pentanediamine, hexanediamine, heptanediamine, octanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, hexadecanediamine, octadecanediamine, octadecenediamine, eicosandiamine, docosandiamine and diamines derived from fatty acids.

[0103] When the diamine is aliphatic and branched, it may include one or more methyl or ethyl substituents on the main chain. For example, the Cc diamine may advantageously be selected from 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 1,3-diaminopentane, 2-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine.

[0104] When the Cc diamine is alicyclic, it is 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), p-bis(aminocyclohexyl)-methane (PACM) and isopropylidene di(cyclohexylamine) (PACP), 1,3-bis(aminomethyl)cyclohexane (1,3-BAC), 1,4-bis(aminomethyl)cyclohexane (1,4-BAC) and mixtures thereof. It may also contain the following carbon skeletons: norbornylmethane, cyclohexylmethane, dicyclohexylpropane, di(methylcyclohexyl), di(methylcyclohexyl)propane. A non-exhaustive list of these cycloaliphatic diamines is given in the publication “Cycloaliphatic Amines” (Encyclopaedia of Chemical Technology, Kirk-Othmer, 4th edition (1992), pages 386-405).

[0105] When the Cc diamine is arylaliphatic, it is selected from 1,3-xylylenediamine and 1,4-xylylenediamine.

[0106] The Cd dicarboxylic acid is selected from the group consisting of linear or branched aliphatic diacids, alicyclic diacids and aromatic diacids.

[0107] When the Cd diacid is aliphatic and linear, it is selected from succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, octadecenedioic acid, eicosanedioic acid, docosanedioic acid and a fatty acid dimer containing 36 carbons.

[0108] The fatty acid dimers mentioned above are dimerized fatty acids obtained by oligomerization or polymerization of unsaturated long-chain hydrocarbon monofatty acids, such as linoleic acid and oleic acid, as described in particular in document EP 0,471,566.

[0109] When the diacid is alicyclic, it may comprise the following carbon skeleton: norbornylmethane, cyclohexylmethane, dicyclohexylmethane, dicyclohexylpropane, di(methylcyclohexyl), di(methylcyclohexyl)propane.

[0110] When the diacid is aromatic, it is chosen from terephthalic acid (denoted by T), isophthalic acid (denoted by I) and naphthalene diacids (denoted by N).

[0111] Excluding caprolactam or aminocaproic acid from the definition of lactam and amino acid in Z means that A and X 1Y is the formula 6 / A / X as defined above 1 Compounds of Y are excluded.

[0112] When the Cc diamine is a C6 diamine, terephthalic acid is excluded from the definition of Cd diacid, which means that A and X are 1 Y is the formula 6T / A / X as defined above 1 Compounds of Y are excluded.

[0113] In one embodiment, the copolyamide consists only of the formula A / X 1 It is composed of three units of Y / Z.

[0114] These three units are as defined above, and the exclusions apply as well.

[0115] Therefore, in this embodiment, there are only three different units A, X 1 Y and Z, but despite this, there may be one or more A units, one or more X 1 Y unit and one or more Z units.

[0116] In another embodiment, the copolyamide consists only of the formula A / X 1 Y / Z three units, and in the formula A / X 1 There is only one A unit and one X in Y / Z 1 Y unit and a Z unit.

[0117] In yet another embodiment, the present invention relates to the use of a copolyamide as defined above for the preparation of a composition as defined above, said composition comprising up to 70% by weight of reinforcing fibers, in particular 30-70% by weight of reinforcing fibers.

[0118] According to one embodiment, the composition comprises 35-65% and preferably 50-65% by weight of reinforcing fibers relative to the total weight of the composition.

[0119] Throughout the specification, the phrase "between ... and " is intended to include the endpoints.

[0120] The composition according to the invention may comprise short reinforcing fibres or short strengthening fibres.

[0121] Preferably, the fibres are short and are 2-13 mm long, preferably 3-8 mm long, prior to application of the composition.

[0122] These short reinforcing fibers can be selected from:

[0123] -Natural fibers

[0124] - Mineral fibers, ie those fibers having a high melting temperature Tm' which is higher than the melting temperature Tm of the semicrystalline copolyamides of the invention and higher than the polymerization and / or implementation temperature.

[0125] - polymer fibers having a melting temperature Tm' or, in the absence of Tm', a glass transition temperature Tg', which is higher than the polymerization temperature or higher than the melting temperature Tm of the semicrystalline copolyamide constituting the thermoplastic matrix and higher than the implementation temperature.

[0126] - or a mixture of the above fibers.

[0127] Examples of mineral fibers suitable for use in the present invention are: carbon fibers, including fibers of nanotubes or carbon nanotubes (CNT), carbon nanofibers or graphene; silica fibers such as glass fibers, in particular E, R, S2 or T types; boron fibers; ceramic fibers, in particular silicon carbide fibers, boron carbide fibers, boron carbonitride fibers, silicon nitride fibers, boron nitride fibers, basalt fibers or basalt-based fibers; fibers or filaments containing metals and / or alloys thereof; metal oxide fibers, in particular aluminum oxide (Al2O3) fibers. 2 O 3 ) fibers; metallized fibers, such as metallized glass fibers and metallized carbon fibers or a mixture of the above fibers.

[0128] More particularly, the fibers may be selected as follows:

[0129] The mineral fibers may be selected from: carbon fibers, carbon nanotube fibers, glass fibers, in particular E, R, S2 or T type, boron fibers, ceramic fibers, in particular silicon carbide fibers, boron carbide fibers, boron carbonitride fibers, silicon nitride fibers, boron nitride fibers, basalt fibers or basalt-based fibers; fibers or filaments containing metals and / or alloys thereof, containing metal oxides such as Al 2 O 3 Fibers of metallized fibers such as metallized glass fibers and metallized carbon fibers or mixtures thereof, and

[0130] - Under the above conditions, the polymer fiber is selected from:

[0131] - thermosetting polymer fibers and more particularly chosen from: unsaturated polyesters, epoxies, vinyl esters, phenolic resins, polyurethanes, cyanoacrylates and polyimides, such as bismaleimide resins, aminoplasts resulting from the reaction of amines such as melamine with aldehydes such as glyoxal or formaldehyde,

[0132] - fibers of thermoplastic polymers and more particularly chosen from: polyethylene terephthalate (PET), polybutylene terephthalate (PBT),

[0133] - Polyamide fibers,

[0134] - Aramid fibers (e.g. ) and aromatic polyamides such as those having one of the following formulae: PPD.T, MPD.I, PAA and PPA, wherein PPD and MPD are p-phenylenediamine and m-phenylenediamine, respectively, PAA is polyaramid and PPA is polyphthalamide,

[0135] - Fibers of polyamide block copolymers, for example polyamide / polyether, fibers of polyaryletherketone (PAEK), for example polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyetherketoneetherketoneketone (PEKEKK).

[0136] Preferred short reinforcing fibers are short fibers selected from the group consisting of carbon fibers, including metallized fibers, glass fibers, including metallized glass fibers such as E, R, S2 or T, aramid fibers (e.g. ) or aromatic polyamide, polyaryletherketone (PAEK) fibers, such as polyetheretherketone (PEEK), polyetherketoneketone (PEKK) fibers, polyetherketoneetherketoneketone (PEKEKK) fibers or mixtures thereof.

[0137] More particularly, the natural fibers are chosen from flax fibers, castor fibers, wood fibers, sisal fibers, kenaf fibers, coir fibers, hemp fibers and jute fibers.

[0138] Advantageously, the weight ratio of reinforcing fibers to copolyamide does not exceed 1.75, in particular 1.6.

[0139] Glass fibers within the meaning of the present invention are understood to be any glass fibers, in particular the glass fibers described by Frederick T. Wallenberger, James C. Watson and Hong Li, PPG industries Inc. (ASM Handbook, Vol 21: composites (#06781G), 2001 ASM International).

[0140] The reinforcing fibers may be:

[0141] - or have a circular cross section with a diameter of 4-25 μm, preferably 4-15 μm.

[0142] - or having a non-circular cross section with an L / D ratio (wherein L represents the largest dimension of the cross section of the fiber and D represents the smallest dimension of the cross section of said fiber) of 2 to 8, in particular 2 to 4. L and D can be measured by scanning electron microscopy (SEM).

[0143] Advantageously, the reinforcing fibers are selected from glass fibers, carbon fibers, and mixtures thereof.

[0144] Advantageously, the reinforcing fibers are selected from glass fibers having a non-circular cross section, glass fibers having a circular cross section, carbon fibers, and mixtures thereof.

[0145] Advantageously, the reinforcing fibers are selected from glass fibers having a non-circular cross section, glass fibers having a circular cross section, and mixtures thereof.

[0146] Advantageously, the reinforcing fibers are glass fibers having a non-circular cross-section.

[0147] Advantageously, the reinforcing fibers are glass fibers having a non-circular cross section and an elastic modulus lower than 76 GPa measured according to ASTM C1557-03.

[0148] In one embodiment, the composition does not contain at least one ingredient selected from the group consisting of polyphenylene ether (PPE), anti-drip agents, PA46, PA66, PA6, polyamides based on units obtained by polycondensation of caprolactam, free radical inhibitors, in particular inorganic, flame retardants, aniline black, elemental iron, polyols, metal oxides selected from magnesium oxide, zinc oxide, calcium oxide or mixtures thereof, amino acid heat stabilizers, amino acid heat stabilizers having at least one hydroxyl group and amorphous polyamides.

[0149] In one embodiment, if the composition comprises titanium oxide, it does not contain metal oxides selected from magnesium oxide, zinc oxide, calcium oxide, or mixtures thereof.

[0150] In another embodiment, the composition comprises, in addition to the copolyamide and the reinforcing fibers:

[0151] - 0 to 10% by weight of at least one impact modifier;

[0152] - 0-20% by weight of at least one filler; and

[0153] - 0-5% by weight of at least one fluidizing agent; and

[0154] - 0 to less than 2%, preferably 0.5 to less than 2% by weight of additives,

[0155] The sum of the copolyamide, reinforcing fibers, impact modifiers, fillers, fluidizing agents and additives is equal to 100%.

[0156] In this latter embodiment, advantageously, the composition does not contain at least one excluded ingredient as defined above.

[0157] In one embodiment, the present invention thus relates to the formula A / X as defined above 1 Y contains at least two different units A and X1 Use of a copolyamide of Y for preparing a composition, the composition comprising:

[0158] - 35-70%, in particular 35-50 and more particularly 38-50% by weight of at least one copolyamide as defined above,

[0159] - 30-70% by weight of reinforcing fibers,

[0160] - 0 to 10% by weight of at least one impact modifier;

[0161] - 0-20% by weight of at least one filler; and

[0162] - 0-5% by weight of at least one fluidizing agent; and

[0163] - 0 to less than 2%, preferably 0.5 to less than 2% by weight of additives,

[0164] The sum of copolyamide, reinforcing fibers, impact modifiers, fillers, fluidizers and additives is equal to 100%,

[0165] And the modulus of the composition does not vary by more than 20% in the temperature range of 20°C to 40°C, in particular in the temperature range of 0°C to 40°C, in particular in the temperature range of -10°C to 40°C, as defined above.

[0166] In another embodiment, the present invention thus relates to the formula A / X as defined above 1 Y contains at least two different units A and X 1 Use of a copolyamide of Y for preparing a composition, the composition comprising:

[0167] - 35-70%, in particular 35-50 and more particularly 38-50% by weight of at least one copolyamide as defined above,

[0168] - 35-65% and preferably 50-65% by weight of reinforcing fibers,

[0169] - 0 to 10% by weight of at least one impact modifier;

[0170] - 0-20% by weight of at least one filler; and

[0171] - 0-5% by weight of at least one fluidizing agent; and

[0172] - 0 to less than 2%, preferably 0.5 to less than 2% by weight of additives,

[0173] wherein the sum of the copolyamide, reinforcing fibers, impact modifiers, fillers, fluidizers and additives is equal to 100%, and the modulus of the composition does not vary by more than 20% in the temperature range of 20°C to 40°C, in particular in the temperature range of 0°C to 40°C, in particular in the temperature range of -10°C to 40°C, as defined above.

[0174] Advantageously, the present invention thus relates to the formula A / X as defined above 1 Y contains at least two different units A and X 1 Use of a copolyamide of Y for preparing a composition, the composition comprising:

[0175] - 35-70%, in particular 35-50 and more particularly 38-50% by weight of at least one copolyamide as defined above,

[0176] - 35-65% and preferably 50-65% by weight of reinforcing fibers,

[0177] - 0 to 10% by weight of at least one impact modifier;

[0178] - 0-20% by weight of at least one filler; and

[0179] - 0-5% by weight of at least one fluidizing agent; and

[0180] - 0 to less than 2%, preferably 0.5 to less than 2% by weight of additives,

[0181] wherein the sum of the copolyamide, reinforcing fibers, impact modifiers, fillers, fluidizers and additives is equal to 100%, and the modulus of the composition does not vary by more than 20% in the temperature range of 20°C to 40°C, in particular in the temperature range of 0°C to 40°C, in particular in the temperature range of -10°C to 40°C, as defined above.

[0182] More advantageously, the present invention thus relates to the formula A / X as defined above 1 Y contains at least two different units A and X 1 Use of a copolyamide of Y for preparing a composition, the composition comprising:

[0183] - 35-65%, in particular 35-50 and more particularly 38-50% by weight of at least one copolyamide as defined above,

[0184] - 35-65% and preferably 50-65% by weight of reinforcing fibers, in particular 50-62% by weight of reinforcing fibers,

[0185] - 0 to 10% by weight of at least one impact modifier;

[0186] - 0-20% by weight of at least one filler; and

[0187] - 0-5% by weight of at least one fluidizing agent; and

[0188] - 0 to less than 2%, preferably 0.5 to less than 2% by weight of additives,

[0189] wherein the sum of the copolyamide, reinforcing fibers, impact modifiers, fillers, fluidizers and additives is equal to 100%, and the modulus of the composition does not vary by more than 20% in the temperature range of 20°C to 40°C, in particular in the temperature range of 0°C to 40°C, in particular in the temperature range of -10°C to 40°C, as defined above.

[0190] In yet another embodiment, the composition consists of a copolyamide, reinforcing fibers, and:

[0191] - 0 to 10% by weight of at least one impact modifier;

[0192] - 0-20% by weight of at least one filler; and

[0193] - 0-5% by weight of at least one fluidizing agent; and

[0194] - 0 to less than 2%, preferably 0.5 to less than 2% by weight of additives,

[0195] The sum of the copolyamide, reinforcing fibers, impact modifiers, fillers, fluidizing agents and additives is equal to 100%.

[0196] In the latter embodiment, the composition therefore does not comprise said previously defined and excluded ingredients.

[0197] Advantageously, in this other embodiment, the present invention thus relates to the formula A / X as defined above 1 Y contains at least two different units A and X 1 The invention relates to a method for preparing a composition comprising the following components:

[0198] - 35-70%, in particular 35-50 and more particularly 38-50% by weight of at least one copolyamide as defined above,

[0199] - 30-70% by weight of reinforcing fibers,

[0200] - 0 to 10% by weight of at least one impact modifier;

[0201] - 0-20% by weight of at least one filler; and

[0202] - 0-5% by weight of at least one fluidizing agent; and

[0203] - 0 to less than 2%, preferably 0.5 to less than 2% by weight of additives,

[0204] wherein the sum of the copolyamide, reinforcing fibers, impact modifiers, fillers, fluidizers and additives is equal to 100%, and the modulus of the composition does not vary by more than 20% in the temperature range of 20°C to 40°C, in particular in the temperature range of 0°C to 40°C, in particular in the temperature range of -10°C to 40°C, as defined above.

[0205] Advantageously, in this other embodiment, the present invention thus relates to the formula A / X as defined above 1 Y contains at least two different units A and X 1 The invention relates to a method for preparing a composition comprising the following components:

[0206] - 35-70%, in particular 35-50 and more particularly 38-50% by weight of at least one copolyamide as defined above,

[0207] - 35-65% and preferably 50-65% by weight of reinforcing fibers,

[0208] - 0 to 10% by weight of at least one impact modifier;

[0209] - 0-20% by weight of at least one filler; and

[0210] - 0-5% by weight of at least one fluidizing agent; and

[0211] - 0 to less than 2%, preferably 0.5 to less than 2% by weight of additives,

[0212] wherein the sum of the copolyamide, reinforcing fibers, impact modifiers, fillers, fluidizers and additives is equal to 100%, and the modulus of the composition does not vary by more than 20% in the temperature range of 20°C to 40°C, in particular in the temperature range of 0°C to 40°C, in particular in the temperature range of -10°C to 40°C, as defined above.

[0213] Advantageously, the present invention thus relates to the formula A / X as defined above 1 Y contains at least two different units A and X 1 The invention relates to a method for preparing a composition comprising the following components:

[0214] - 35-65%, in particular 35-50 and more particularly 38-50% by weight of at least one copolyamide as defined above,

[0215] - 35-65% and preferably 50-65% by weight of reinforcing fibers, in particular 50-62% by weight of reinforcing fibers,

[0216] - 0 to 10% by weight of at least one impact modifier;

[0217] - 0-20% by weight of at least one filler; and

[0218] - 0-5% by weight of at least one fluidizing agent; and

[0219] - 0 to less than 2%, preferably 0.5 to less than 2% by weight of additives,

[0220] wherein the sum of the copolyamide, reinforcing fibers, impact modifiers, fillers, fluidizers and additives is equal to 100%, and the modulus of the composition does not vary by more than 20% in the temperature range of 20°C to 40°C, in particular in the temperature range of 0°C to 40°C, in particular in the temperature range of -10°C to 40°C, as defined above.

[0221] The expression "impact modifier" means a polymer based on polyolefins, in particular polyolefins, having a flexural modulus lower than 100 MPa, measured according to Standard ISO 178:2010 (23°C RH50), and a Tg lower than 0°C (measured at the level of the inflection point of the DSC thermogram according to Standard 11357-2:2013).

[0222] The impact modifier may also be a PEBA block polymer (polyether-block-amide) having a flexural modulus <200 MPa.

[0223] The composition may further comprise one or more impact modifiers as defined above. The presence of an impact modifier makes it possible to impart greater ductility to the manufactured article.

[0224] The polyolefin of the impact modifier may be functionalized or unfunctionalized, or may comprise both in a mixture.

[0225] When the polyolefin is functionalized, some or all of the polyolefin carries functional groups selected from carboxylic acid, carboxylic anhydride and epoxy functions. The functional groups 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, ethylene-higher olefin copolymers, in particular ethylene-octene copolymers, ethylene-alkyl acrylate-maleic anhydride terpolymers.

[0226] PEBA (polyether block amide) is a copolymer containing polyamide and polyether blocks. They may also contain ester functional groups, in particular ester functional groups obtained by condensation reaction of terminal carboxyl functions of the polyamide blocks with hydroxyl functions of the polyether blocks. PEBA is commercially available, in particular by the company Arkema under the trade name

[0227] Advantageously, the impact modifier is selected from: Fusabond F493, Tafmer MH5020, in particular 40R53SP01, VA1803 or VA1801, IM800 or a mixture thereof, in which case the ratio ranges from 0.1 / 99.9 to 99.9 / 0.1.

[0228] The impact modifier may also be a core-shell modifier, also denoted as a core-shell polymer. The "core-shell modifier" is present in the form of fine particles having an elastomeric core and at least one thermoplastic shell; the particle size is generally less than a micron and advantageously 150-500 nm, including the end values. The core-shell modifier has an acrylic or butadiene matrix.

[0229] A variety of different impact modifiers may be present in the composition.

[0230] According to certain embodiments, the content of the impact modifier may be 0-10% by weight, advantageously 1-10% by weight relative to the total weight of the composition.

[0231] According to one embodiment, the composition comprises 1 to 8% and in particular 2 to 5% by weight of impact modifier relative to the total weight of the composition.

[0232] In another embodiment, the impact modifier may be present in the composition in an amount of 1-2% by weight; or 2-3% by weight; or 3-4% by weight; or 4-5% by weight; or 6-7% by weight; or 7-8% by weight; or 8-9% by weight; or 9-10% by weight.

[0233] About filler

[0234] The composition may also contain fillers. Contemplated fillers include conventional mineral fillers, such as kaolin, magnesia, slag, carbon black, expanded or unexpanded graphite, wollastonite, nucleating agents such as silica, alumina, clay or talc, in particular talc, pigments such as titanium oxide and zinc sulfide, and antistatic fillers.

[0235] The composition may also contain a fluidizing agent.

[0236] The term "fluidizing agent" particularly includes prepolymers.

[0237] The prepolymer may be selected from linear or branched aliphatic, alicyclic, semiaromatic or even 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 1000-10000 g / mol, in particular 1000-5000 g / mol. In particular, if the chain limiter used is, for example, a monoamine, the prepolymer may be a monofunctional NH 2 The number average molecular weight (Mn) or amine number is calculated according to the following formula: Mn = 1000 / [NH 2 ], where [NH 2 ] is the concentration of amine functional groups in the copolyamide as determined, for example, by potentiometric titration.

[0238] According to certain embodiments, the content of the fluidizing agent relative to the total weight of the composition may be 0-5% by weight, in particular 1-5% by weight, and especially 1-5%.

[0239] According to one embodiment, the composition comprises 1-4% and in particular 2-3% by weight of fluidizing agent relative to the total weight of the composition.

[0240] According to another embodiment, the content of the fluidizing 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.

[0241] The term "additive" means dyes, stabilizers, surfactants, brighteners, antioxidants, lubricants, plasticizers, waxes and mixtures thereof.

[0242] Advantageously, this means dyes, stabilizers, surfactants, brighteners, antioxidants, lubricants, waxes and mixtures thereof.

[0243] The stabilizer may be an organic or inorganic stabilizer. Typical stabilizers used with polymers are, for example, phenols, phosphites, UV absorbers, HALS (hindered amine light stabilizer) type stabilizers and metal iodides. Examples include BASF's 1010, 245, 1098, from BASF 168, 126, from BASF 312, 770, Iodide P201 from Ciba, and S-EED.

[0244] The lubricant may be, inter alia, a stearate or a wax binder.

[0245] The wax may especially be an amorphous wax such as beeswax, silicone wax, polyethylene wax, oxidized polyethylene wax, ethylene copolymer wax, montan wax and polyether wax.

[0246] A variety of different additives of the same or different classes may be present in the composition.

[0247] The additive content is 0 to less than 2% by weight relative to the total weight of the composition.

[0248] According to one embodiment, the composition comprises from 0.1 to less than 2% and in particular from 0.5 to less than 2% by weight of additives relative to the total weight of the composition.

[0249] According to some embodiments, the additive content in the composition may be 0-0.5% by weight; or 0.1-0.5% by weight; or 0.5-1% by weight; or 1-1.5% by weight; or 1.5-less than 2% by weight.

[0250] According to a second aspect, the present invention relates to a composition, in particular a composition for injection molding, comprising:

[0251] - 35-70%, in particular 35-50 and more particularly 38-50% by weight of at least one copolyamide as defined above,

[0252] - 30-65, in particular 50-65 and more particularly 50-62% by weight of reinforcing fibers;

[0253] - 0 to 10% by weight of at least one impact modifier;

[0254] - 0-20% by weight of at least one filler; and

[0255] - 0-5% by weight of at least one fluidizing agent; and

[0256] - 0 to less than 2%, preferably 0.1 to less than 2%, in particular 0.5 to less than 2% by weight of additives,

[0257] The condition is that when the cross section of the reinforcing fiber is non-circular and has a diameter of 1.5-5.0×10 -6 cm 2 When the cross-sectional area is 1.50 mm / s, the weight ratio of the reinforcing fibers to the copolyamide is not more than 1.75, in particular 1.6;

[0258] The sum of the proportions of the individual components of the composition is equal to 100%.

[0259] Therefore, for the 1.5-5.0×10 -6 cm2 The exclusion of non-circular cross-sectional reinforcing fibers having a cross-sectional area of ​​1.75 is effective for both a ratio of 1.6 and a ratio of 1.75.

[0260] In one embodiment, the composition, which is particularly useful for injection molding, comprises:

[0261] - 35-70%, in particular 35-50 and more particularly 38-50% by weight of at least one copolyamide as defined above,

[0262] - 30-65, in particular 50-65 and more particularly 50-62% by weight of reinforcing fibers;

[0263] - 0 to 10% by weight of at least one impact modifier;

[0264] - 0-20% by weight of at least one filler; and

[0265] - 0-5% by weight of at least one fluidizing agent; and

[0266] - 0 to less than 2%, preferably 0.1 to less than 2%, in particular 0.5 to less than 2% by weight of additives,

[0267] Provided that, when the reinforcing fibers have a non-circular cross-section, the weight ratio of the reinforcing fibers to the copolyamide does not exceed 1.75, in particular 1.6;

[0268] The sum of the proportions of the individual components of the composition is equal to 100%.

[0269] Thus, the exclusion of the non-circular cross-section reinforcing fibers is effective for both a ratio of 1.75 and a ratio of 1.6.

[0270] In another embodiment, the polymer particularly useful for injection molding comprises:

[0271] - 35-70%, in particular 35-50 and more particularly 38-50% by weight of at least one copolyamide as defined above,

[0272] - 30-65, in particular 50-65 and more particularly 50-62% by weight of reinforcing fibers;

[0273] - 0 to 10% by weight of at least one impact modifier;

[0274] - 0-20% by weight of at least one filler; and

[0275] - 0-5% by weight of at least one fluidizing agent; and

[0276] - 0 to less than 2%, preferably 0.1 to less than 2%, in particular 0.5 to less than 2% by weight of additives, provided that the weight ratio of reinforcing fibers to copolyamide does not exceed 1.75, in particular 1.6;

[0277] The sum of the proportions of the individual components of the composition is equal to 100%.

[0278] The reinforcing fibers, impact modifiers, fillers, fluidizing agents and additives are as defined above, and all concentration ranges defined above concerning the impact modifiers, fluidizing agents, fillers and additives are also valid for the composition itself.

[0279] The exclusions defined above also apply for the preparation of the compositions.

[0280] Advantageously, the composition, which is particularly useful for injection molding, consists of the following ingredients:

[0281] - 35-70%, in particular 35-50 and more particularly 38-50% by weight of at least one copolyamide as defined above,

[0282] - 30-65, in particular 50-65 and more particularly 50-62% by weight of reinforcing fibers;

[0283] - 0 to 10% by weight of at least one impact modifier;

[0284] - 0-20% by weight of at least one filler; and

[0285] - 0-5% by weight of at least one fluidizing agent; and

[0286] - 0 to less than 2%, preferably 0.1 to less than 2%, in particular 0.5 to less than 2% by weight of additives,

[0287] Provided that, when the reinforcing fiber has a non-circular cross section and has a -6 cm 2 When the cross-sectional area is 1.50 mm / s, the weight ratio of the reinforcing fibers to the copolyamide is not more than 1.75, in particular 1.6;

[0288] The sum of the proportions of the individual components of the composition is equal to 100%.

[0289] Therefore, for the 1.5-5.0×10 -6 cm 2 The exclusion of non-circular cross-sectional reinforcing fibers having a cross-sectional area of ​​1.75 is effective for both a ratio of 1.6 and a ratio of 1.75.

[0290] In one embodiment, the composition, which is particularly useful for injection molding, consists of the following ingredients:

[0291] - 35-70%, in particular 35-50 and more particularly 38-50% by weight of at least one copolyamide as defined above,

[0292] - 30-65, in particular 50-65 and more particularly 50-62% by weight of reinforcing fibers;

[0293] - 0 to 10% by weight of at least one impact modifier;

[0294] - 0-20% by weight of at least one filler; and

[0295] - 0-5% by weight of at least one fluidizing agent; and

[0296] - 0 to less than 2%, preferably 0.1 to less than 2%, in particular 0.5 to less than 2% by weight of additives,

[0297] Provided that, when the reinforcing fibers have a non-circular cross-section, the weight ratio of the reinforcing fibers to the copolyamide does not exceed 1.75, in particular 1.6;

[0298] The sum of the proportions of the individual components of the composition is equal to 100%.

[0299] Thus, the exclusion of the non-circular cross-section reinforcing fibers is effective for both a ratio of 1.75 and a ratio of 1.6.

[0300] In another embodiment, the composition, which is particularly useful for injection molding, consists of the following ingredients:

[0301] - 35-70%, in particular 35-50 and more particularly 38-50% by weight of at least one copolyamide as defined above,

[0302] - 30-65, in particular 50-65 and more particularly 50-62% by weight of reinforcing fibers;

[0303] - 0 to 10% by weight of at least one impact modifier;

[0304] - 0-20% by weight of at least one filler; and

[0305] - 0-5% by weight of at least one fluidizing agent; and

[0306] - 0 to less than 2%, preferably 0.1 to less than 2%, in particular 0.5 to less than 2% by weight of additives, provided that the weight ratio of reinforcing fibers to copolyamide does not exceed 1.75, in particular 1.6;

[0307] The sum of the proportions of the individual components of the composition is equal to 100%.

[0308] Advantageously, the copolyamide of the composition is chosen from PA11 / 10T, PA11 / 12T, PA12 / 10T, PA12 / 12T, PA1010 / 10T, PA1012 / 10T, PA1010 / 12T, PA1012 / 12T, PA1210 / 10T, PA1212 / 10T, PA1210 / 12T, PA1212 / 12T, in particular PA11 / 10T.

[0309] In one embodiment, the reinforcing fibers of the composition are selected from glass fibers, carbon fibers and mixtures thereof, in particular glass fibers.

[0310] Advantageously, the glass fibers of the composition are selected from glass fibers with non-circular cross-section and glass fibers with circular cross-section, carbon fibers and mixtures thereof, in particular glass fibers with non-circular cross-section and glass fibers with circular cross-section and mixtures thereof, in particular glass fibers with non-circular cross-section.

[0311] Glass fibers are as defined above.

[0312] According to a third aspect, the invention relates to a process for manufacturing a composition as defined above, wherein the ingredients of said composition are mixed by compounding, in particular in a twin-screw extruder, preferably a co-rotating extruder, a blender or an internal mixer.

[0313] Finally, according to a fourth aspect, the invention relates to a moulding obtainable by injection moulding from the composition defined above.

[0314] Advantageously, the molded article is used for electrical applications and electronic devices and is in particular chosen from televisions, digital cameras, digital game consoles, telephone parts, digital tablets, drones, printers or computer parts. Example

[0315] The present invention will be explained in more detail in the following examples.

[0316] Example 1: Synthesis of the copolyamide of the present invention.

[0317] Various polyamides (comparative) and copolyamides of the invention were prepared according to conventional techniques for the synthesis of polyamides and copolyamides.

[0318] Synthesis of CoPa 11 / 10T representatives of various copolyamides:

[0319] In the reactor, aminoundecanoic acid, decanediamine and terephthalic acid monomers are loaded together according to the required mass ratio. First, the medium is inertized to remove oxygen that can produce yellowing or side reactions. Water can also be loaded to improve heat exchange. Two platforms of temperature and pressure increase are carried out. Temperature (T°) and pressure conditions are selected to allow the medium to melt. After reaching the maintenance conditions, degassing is carried out to allow the polycondensation reaction to proceed. The medium gradually becomes viscous, and nitrogen purging or applying vacuum causes the formation of reaction water. When the stop conditions related to the required viscosity are reached, stirring is stopped and extrusion and granulation can be started. The particles obtained are then compounded with glass fibers.

[0320] Compounding

[0321] The composition was prepared by mixing the polymer granules with the short fibers while molten. The mixture was produced by compounding on a twin-screw co-rotating MC26 type extruder with a flat temperature profile (T°) at 290° C. The screw speed was 250 rpm and the flow rate was 20 kg / h.

[0322] The glass fibers are introduced via a side feed.

[0323] Additives and fillers are added in the main hopper during the compounding process.

[0324] The following compositions were prepared (E = Example according to the invention CE = Comparative Example):

[0325] Table 1

[0326]

[0327]

[0328] 245 and 168 as antioxidant

[0329] CSX 451J circular cross-section fibers and CSG 3PA820 non-circular cross-section fibers (also known as flat fibers) are sold by Nittobo Corporation.

[0330] injection

[0331] Preparation of 100*100*1mm by injection of different compositions 3 Plate material:

[0332] -Injection temperature: 300℃

[0333] -Molding temperature: 80℃

[0334] The circulation time is adjusted according to the composition to allow injection of the composition and is less than 50 seconds.

[0335] Example 2: Change in flexural modulus after water absorption

[0336] In order to evaluate the effect of moisture on the flexural modulus, the flexural modulus of the specimens of the obtained compositions were measured on an Instron 5966 machine manufactured by Instron Corporation. The compositions were dry compositions and compositions previously saturated in water at 65°C.

[0337] The tests were carried out at different temperatures ranging from -10°C to 60°C.

[0338] From the injection-moulded plaques, test specimens were cut out in the injection direction having the dimensions according to ISO 178 but with a thickness of 1 mm.

[0339] The results are shown in Table 2-8 below:

[0340] Table 2:

[0341]

[0342] Table 3

[0343]

[0344] Table 4

[0345]

[0346] Table 5

[0347]

[0348]

[0349] Table 6

[0350]

[0351] Table 7

[0352]

[0353] Table 8

[0354]

[0355]

[0356] Table 9

[0357]

[0358] Table 10

[0359]

[0360] Table 11

[0361]

[0362] Example 3: Change in tensile modulus after water absorption

[0363] In order to evaluate the effect of moisture on the tensile modulus, the tensile modulus of specimens of the obtained compositions, both dry compositions and compositions previously saturated in water at 65° C., were measured on an Instron 5966 machine manufactured by the company Instron.

[0364] The tests were carried out at different temperatures ranging from -10°C to 60°C.

[0365] From the injection-moulded plaques, test specimens were cut out in the injection direction having the dimensions according to ISO 527 but with a thickness of 1 mm.

[0366] For the tensile modulus, the same trends as those observed for the flexural modulus were found.

[0367] Tables 2-8 and Example 3 show that the compositions of the invention have higher modulus stability than comparative compositions CE1 and CE2 for both flexure and tension.

Claims

1. Use of a copolyamide of the formula A / X1Y comprising at least two different units A and X1Y for preparing a composition having a high modulus stability under the influence of temperature and humidity, wherein: - A is a repeating unit obtained by polycondensation of: At least one C9-C 18 Amino acids, or At least one C9-C 18 lactam, or At least one C4-C 36 diamine Ca and at least one C4-C 36 Dicarboxylic acid Cb; The at least one diamine Ca is a linear or branched aliphatic diamine, and the at least one Cb diacid is a linear or branched aliphatic diacid, - X1Y is composed of at least one C9-C 18 Repeating units obtained by polycondensation of a linear aliphatic diamine X1 and at least one aromatic dicarboxylic acid Y, The composition comprises 35-65% by weight of reinforcing fibers relative to the total weight of the composition, and the flexural modulus or the tensile modulus of the composition measured after the same conditioning does not vary by more than 20% in the temperature range of 20°C to 40°C, wherein the composition further comprises a fluidizing agent, Wherein the fluidizing agent comprises a prepolymer, The prepolymer is monofunctional NH2. The content of the fluidizing agent relative to the total weight of the composition is 1-5% by weight.

2. The use according to claim 1, wherein C9-C 18 Amino acid is C 10 -C 18 Amino acids.

3. The use according to claim 2, wherein C 10 -C 18 Amino acid is C 10 -C 12 Amino acids.

4. The use according to claim 1, wherein C9-C 18 Lactam is C 10 -C 18 Lactam.

5. The use according to claim 4, wherein C 10 -C 18 Lactam is C 10 -C 12 Lactam.

6. The use according to claim 1, wherein C4-C 36 Diamine Ca is C6-C 18 Diamine Ca.

7. The use according to claim 6, wherein C6-C 18 Diamine Ca is C6-C 12 Diamine Ca.

8. The use according to claim 7, wherein C6-C 12 Diamine Ca is C 10 -C 12 Diamine Ca.

9. The use according to claim 1, wherein C4-C 36 Dicarboxylic acid Cb is C6-C 18 Dicarboxylic acid Cb.

10. The use according to claim 9, wherein C6-C 18 Dicarboxylic acid Cb is C6-C 12 Dicarboxylic acid Cb.

11. The use according to claim 10, wherein C6-C 12 Dicarboxylic acid Cb is C 10 -C 12 Dicarboxylic acid Cb.

12. The use according to claim 1, wherein C9-C 18 The linear aliphatic diamine X1 is C 10 -C 18 Linear aliphatic diamine X1.

13. The use according to claim 12, wherein C 10 -C 18 The linear aliphatic diamine X1 is C 10 -C 12 Linear aliphatic diamine X1.

14. The use according to claim 1, wherein the composition comprises 50-65% by weight of reinforcing fibers.

15. The use according to claim 1, wherein the flexural modulus or the tensile modulus measured after the same conditioning does not vary by more than 20% in the temperature range of 0°C to 40°C.

16. The use according to claim 1, wherein the flexural modulus or tensile modulus measured after the same conditioning does not vary by more than 20% in the temperature range of -10°C to 40°C.

17. The use according to one of claims 1 to 16, wherein X1Y is composed of at least one C 10 -C 18 The repeating unit is obtained by the polycondensation of an aliphatic diamine X and at least one aromatic dicarboxylic acid Y.

18. The use according to claim 17, wherein C 10 -C 18 Aliphatic diamine X is C 10 -C 12 Aliphatic diamines.

19. The method according to claim 1, wherein Y is terephthalic acid.

20. The use according to one of claims 1 to 16, wherein X1Y is a unit selected from the group consisting of units 10T, 12T and mixtures thereof.

21. The use according to one of claims 1 to 16, wherein in the copolyamide of formula A / X1Y, A is an amino acid or a lactam.

22. The method according to claim 1, wherein in the copolyamide of formula A / X1Y, A is C 11 or C 12 Amino acids or lactams.

23. The use according to any one of claims 1 to 16, wherein the copolyamide is semicrystalline.

24. Use according to claim 23, wherein the copolyamide is semicrystalline having a crystallization enthalpy higher than 30 J / g.

25. The use according to any one of claims 1 to 16, wherein the copolyamide consists exclusively of units A and X1Y of the formula A / X1Y.

26. The method according to claim 1, wherein the copolyamide comprises at least one third unit Z different from the A and X1Y units and conforms to the general formula A / X1Y / Z in: Units A and X1Y are as defined in claim 1, Z is selected from units derived from amino acids, units derived from lactams and units having the formula (Cc diamine).(Cd diacid) wherein c represents the number of carbon atoms in the diamine and d represents the number of carbon atoms in the diacid, c and d are each 4 to 36, Provided that caprolactam or aminocaproic acid are excluded from the definition of lactam and amino acid of Z and when the Cc diamine is a C6 diamine, then terephthalic acid is excluded from the definition of Cd diacid.

27. The use according to claim 26, wherein c and d are each 9-18.

28. The use according to claim 26, wherein the copolyamide consists only of three units of the formula A / X1Y / Z.

29. The use according to claim 28, wherein the reinforcing fibers are selected from glass fibers and carbon fibers or mixtures thereof.

30. The use according to claim 29, wherein the reinforcing fibers are selected from glass fibers.

31. A composition comprising: - 35 to 70% by weight of at least one copolyamide as defined in one of claims 1 to 30, - 35-65% by weight of reinforcing fibers; - 0-10% by weight of at least one impact modifier; - 0-20% by weight of at least one filler; and - 1 to 5% by weight of at least one fluidizing agent; and -0- less than 2% by weight of additives, Provided that when the cross section of the reinforcing fiber is non-circular and has a -6 cm 2 When the cross-sectional area of ​​the reinforcing fiber is greater than 1.75, the weight ratio of the reinforcing fiber to the copolyamide shall not exceed 1.75; The sum of the proportions of the components of the composition is equal to 100%, Wherein the fluidizing agent comprises a prepolymer, The prepolymer is monofunctional NH2.

32. A composition according to claim 31, wherein the composition is useful for injection moulding.

33. The composition according to claim 31, comprising 35 to 50% by weight of at least one copolyamide as defined in one of claims 1 to 30.

34. The composition according to claim 33, comprising 38 to 50% by weight of at least one copolyamide as defined in one of claims 1 to 30.

35. A composition according to claim 31 comprising 50-65% by weight of reinforcing fibers.

36. A composition according to claim 31 comprising 0.1 to less than 2% by weight of an additive.

37. A composition according to claim 36 comprising 0.5 to less than 2% by weight of additives.

38. The composition of claim 31 wherein the weight ratio of reinforcing fiber to copolyamide is no more than 1.

6.

39. according to a composition among the claims 31-38, wherein copolyamide is selected from PA11 / 10T, PA11 / 12T, PA12 / 10T, PA12 / 12T, PA1010 / 10T, PA1012 / 10T, PA1010 / 12T, PA1012 / 12T, PA1210 / 10T, PA1212 / 10T, PA1210 / 12T, PA1212 / 12T.

40. The composition according to claim 39, wherein the copolyamide is selected from PA11 / 10T.

41. A composition according to one of claims 31 to 38, wherein the reinforcing fibers are selected from glass fibers, carbon fibers or mixtures thereof.

42. A composition according to claim 41, wherein the reinforcing fibers are selected from glass fibers.

43. The composition according to claim 41, wherein the glass fibers are selected from the group consisting of glass fibers of non-circular cross-section and glass fibers of circular cross-section, carbon fibers, and mixtures thereof.

44. The composition according to claim 43, wherein the glass fibers are selected from the group consisting of glass fibers having a non-circular cross-section and glass fibers having a circular cross-section and mixtures thereof.

45. The composition according to claim 43, wherein the glass fibers are selected from glass fibers having a non-circular cross-section.

46. ​​A method of making a composition as defined in any one of claims 31 to 45, wherein the ingredients of the composition are mixed by compounding.

47. A method according to claim 46, wherein the ingredients of the composition are mixed by compounding in a twin-screw extruder, a blender or an internal mixer.

48. Moulded article obtained by injection moulding from a composition according to one of claims 31 to 45.

49. Moulded articles according to claim 48 for use in electrical applications and electronic equipment.

50. The molded article according to claim 49, wherein the electrical and electronic applications are selected from a television, a digital camera, a digital game console, a telephone component, a digital tablet, a drone, a printer or a computer component.

Images