Polyamide composition having high modulus and low dielectric constant and use thereof

Abstract

The present invention relates to a polyamide composition having a high modulus and a low dielectric constant and to the use thereof. The invention relates to the use of a mixture of solid and hollow glass reinforcement materials comprising 5 to 50% by weight of hollow glass beads, relative to the sum of the solid and hollow glass reinforcement materials, with an alloy consisting of at least one polyamide and at least one polyolefin, the invention relates to a use for the dry production of a composition at 23 DEG C, said composition having a modulus of at least 8 GPa, in particular at least 10 GPa, in particular at least 11 GPa, and a modulus of at least 10 GPa, in particular at least 11 GPa, at a frequency of at least 1 GHz, in particular at a frequency of at least 2 GHz, in particular at a frequency of at least 3 GHz, at 23 DEG C, according to ASTM D-2520-13. A dielectric constant Dk of less than or equal to 3.5, in particular less than or equal to 3.3, in particular less than or equal to 3.2, measured at 50% RH.

Description

[0001] This application is a divisional application of the patent application with the application number 202080050562.0, the application date of June 10, 2020, the priority date of June 11, 2019, and the invention title of "Polyamide Composition with High Modulus and Low Dielectric Constant and Its Use". Technical Field

[0002] The present invention relates to the use of a mixture of solid and hollow glass reinforcing materials and an alloy (blend) composed of at least one polyamide and at least one polyolefin for manufacturing a composition having a high modulus and a low dielectric constant, a method for manufacturing the same, and the composition. Prior Art

[0003] Original equipment manufacturers (OEMs), especially those in the fields of electronics, telecommunications, or data exchange applications (such as autonomous vehicles or interconnect applications), are increasingly interested in materials with a low dielectric constant for protecting or encapsulating such devices.

[0004] In fact, the advantage of integrating such materials into, for example, the housing of a mobile phone is to ensure the integrity of the signal in antenna applications, thereby ensuring complete and high-speed signal transmission.

[0005] Furthermore, in the case of data exchange, the dielectric constant must be as low as possible to ensure the fastest possible data exchange.

[0006] Therefore, the main challenge for such applications is to have the lowest dielectric properties while maintaining a very rigid protective or encapsulating material. However, in order to obtain a rigid protective or encapsulating material, glass fibers are usually required, which will give the material a higher modulus and thus higher stiffness.

[0007] However, it is well known that the presence of standard glass fibers (such as in a phone housing) ensures good stiffness of the housing, but will also significantly increase the dielectric constant and thus interfere with signal transmission.

[0008] Therefore, there is a need for a material that exhibits both stiffness and thus high modulus properties while maintaining a low dielectric constant, thereby ensuring complete and high-speed signal transmission or the fastest possible data exchange.

[0009] Therefore, the present invention has solved the above problems. The present invention relates to the use of a mixture of solid and hollow glass reinforcing materials and an alloy composed of at least one polyamide and at least one polyolefin, wherein the mixture of solid and hollow glass reinforcing materials contains 5% to 50% by weight, especially 5% to 35% by weight, of hollow glass beads based on the total of the solid and hollow glass reinforcing materials.

[0010] Said use is for dry preparation, at 23 °C, of a composition having a modulus of at least 8 GPa, particularly at least 10 GPa, particularly at least 11 GPa, and a dielectric constant Dk of less than or equal to 3.5, particularly less than or equal to 3.3, particularly less than or equal to 3.2, measured at 23 °C and 50% RH at a frequency of at least 1 GHz, particularly at least 2 GHz, particularly at least 3 GHz, in accordance with ASTM D-2520-13.

[0011] In other words, the present invention relates to the use of a mixture of solid and hollow glass reinforcements and an alloy composed of at least one polyamide and at least one polyolefin, said mixture of solid and hollow glass reinforcements containing 5% to 50% by weight of hollow glass beads, particularly 5% to 35% by weight of hollow glass beads, relative to the total of the solid and hollow glass reinforcements.

[0012] Said use is for at least maintaining the modulus of a composition containing said mixture and said alloy and reducing its dielectric constant, relative to a composition containing said alloy and glass reinforcements without solid glass reinforcements or containing said alloy and glass reinforcements without hollow glass reinforcements, said modulus of said composition in the dry state at 23 °C being at least equal to 8 GPa, particularly at least equal to 10 GPa, particularly at least equal to 11 GPa, and said dielectric constant of said composition being less than or equal to 3.5, particularly less than or equal to 3.3, particularly less than or equal to 3.2, said dielectric constant being measured at 23 °C and 50% RH at a frequency of at least 1 GHz, particularly at least 2 GHz, particularly at least 3 GHz, in accordance with ASTM D-2520-13.

[0013] In one embodiment, the composition of the present invention is free of polyamide 6 and 66.

[0014] The inventors have thus unexpectedly found that the combination of solid and hollow glass reinforcements and an alloy composed of at least one polyamide and at least one polyolefin, and in addition the combination with a specific proportion of hollow glass beads relative to the total of the solid and hollow glass reinforcements, enables the preparation of a composition having a high modulus of at least 8 GPa, particularly at least 10 GPa, particularly at least 11 GPa and a low dielectric constant Dk of less than or equal to 3.5, particularly less than or equal to 3.3, particularly less than or equal to 3.2, thus making it possible to have a rigid material capable of ensuring complete, high-speed signal transmission or having the fastest possible data exchange.

[0015] There are differences between different moduli (such as tensile modulus, flexural modulus, etc.). If we consider the flexural modulus, it is always lower than the tensile modulus.

[0016] These moduli can be affected by temperature and the moisture level in the sample.

[0017] In one embodiment, the moduli defined above correspond to both the flexural modulus and the tensile modulus, the flexural modulus is measured according to ISO 178:2010 and the tensile modulus (or elastic modulus E) is measured according to ISO 527-1 and 2:2012.

[0018] In another embodiment, the moduli defined above correspond to the flexural modulus and are measured as above.

[0019] In another embodiment, the moduli defined above correspond to the tensile modulus and are measured as above.

[0020] The dielectric constant is defined as the ratio of the permittivity (absolute permittivity) ε of the material under consideration to the permittivity of vacuum. It is denoted by k or Dk and is measured according to ASTM D-2520-13. This is the relative dielectric constant.

[0021] It is measured at 23 °C at 50% relative humidity (RH) on a sample that has been pre-dried (especially for 5 days at 80 °C).

[0022] In one embodiment, the composition has a dry modulus at 23 °C of at least 8 GPa, and a dielectric constant Dk of less than or equal to 3.5 at 50% RH at a frequency of at least 1 GHz, and the modulus corresponds to the tensile modulus and the flexural modulus.

[0023] In one embodiment, the composition has a dry modulus at 23 °C of at least 10 GPa and a dielectric constant Dk of less than or equal to 3.5 at 50% RH at a frequency of at least 1 GHz, and the modulus corresponds to the tensile modulus and the flexural modulus.

[0024] In one embodiment, the composition has a dry modulus at 23 °C of at least 11 GPa and a dielectric constant Dk of less than or equal to 3.5 at 50% RH at a frequency of at least 1 GHz, and the modulus corresponds to the tensile modulus and the flexural modulus.

[0025] In one embodiment, the composition has a dry modulus at 23 °C of at least 8 GPa and a dielectric constant Dk of less than or equal to 3.3 at 50% RH at a frequency of at least 1 GHz, and the modulus corresponds to the tensile modulus and the flexural modulus.

[0026] In one embodiment, the composition has a dry modulus at 23 °C of at least 10 GPa and a dielectric constant Dk of less than or equal to 3.3 at 50% RH at a frequency of at least 1 GHz, and the modulus corresponds to the tensile modulus and the flexural modulus.

[0027] In one embodiment, the composition has a dry modulus at 23 °C of at least 11 GPa and a dielectric constant Dk of less than or equal to 3.3 at 50% RH at a frequency of at least 1 GHz, and the modulus corresponds to the tensile modulus and the flexural modulus.

[0028] In one embodiment, the composition has a dry modulus at 23 °C of at least 8 GPa and a dielectric constant Dk of less than or equal to 3.2 at 50% RH at a frequency of at least 1 GHz, and the modulus corresponds to the tensile modulus and the flexural modulus.

[0029] In one embodiment, the composition has a dry modulus at 23 °C of at least 10 GPa and a dielectric constant Dk of less than or equal to 3.2 at 50% RH at a frequency of at least 1 GHz, and the modulus corresponds to the tensile modulus and the flexural modulus.

[0030] In one embodiment, the composition has a dry modulus at 23 °C of at least 11 GPa and a dielectric constant Dk of less than or equal to 3.2 at 50% RH at a frequency of at least 1 GHz, and the modulus corresponds to the tensile modulus and the flexural modulus.

[0031] In one embodiment, the composition has a dry modulus at 23 °C of at least 8 GPa and a dielectric constant Dk of less than or equal to 3.5 at 50% RH at a frequency up to 2.4 GHz, and the modulus corresponds to the tensile modulus and the flexural modulus.

[0032] In one embodiment, the composition has a dry modulus at 23 °C of at least 10 GPa and a dielectric constant Dk of less than or equal to 3.5 at 50% RH at a frequency up to 2.4 GHz, and the modulus corresponds to the tensile modulus and the flexural modulus.

[0033] In one embodiment, the composition has a dry modulus at 23 °C of at least 11 GPa and a dielectric constant Dk of less than or equal to 3.5 at 50% RH at a frequency up to 2.4 GHz, and the modulus corresponds to the tensile modulus and the flexural modulus.

[0034] In one embodiment, the composition has a dry modulus at 23 °C of at least 8 GPa and a dielectric constant Dk of less than or equal to 3.3 at 50% RH at frequencies up to 2.4 GHz, the modulus corresponding to the tensile modulus and the flexural modulus.

[0035] In one embodiment, the composition has a dry modulus at 23 °C of at least 10 GPa and a dielectric constant Dk of less than or equal to 3.3 at 50% RH at frequencies up to 2.4 GHz, the modulus corresponding to the tensile modulus and the flexural modulus.

[0036] In one embodiment, the composition has a dry modulus at 23 °C of at least 11 GPa and a dielectric constant Dk of less than or equal to 3.3 at 50% RH at frequencies up to 2.4 GHz, the modulus corresponding to the tensile modulus and the flexural modulus.

[0037] In one embodiment, the composition has a dry modulus at 23 °C of at least 8 GPa and a dielectric constant Dk of less than or equal to 3.2 at 50% RH at frequencies up to 2.4 GHz, the modulus corresponding to the tensile modulus and the flexural modulus.

[0038] In one embodiment, the composition has a dry modulus at 23 °C of at least 10 GPa and a dielectric constant Dk of less than or equal to 3.2 at 50% RH at frequencies up to 2.4 GHz, the modulus corresponding to the tensile modulus and the flexural modulus.

[0039] In one embodiment, the composition has a dry modulus at 23 °C of at least 11 GPa and a dielectric constant Dk of less than or equal to 3.2 at 50% RH at frequencies up to 2.4 GHz, the modulus corresponding to the tensile modulus and the flexural modulus.

[0040] In one embodiment, the composition has a dry modulus at 23 °C of at least 8 GPa and a dielectric constant Dk of less than or equal to 3.5 at 50% RH at frequencies of at least 1 GHz, the modulus corresponding to the flexural modulus.

[0041] In one embodiment, the composition has a dry modulus at 23 °C of at least 10 GPa and a dielectric constant Dk of less than or equal to 3.5 at 50% RH at frequencies of at least 1 GHz, the modulus corresponding to the flexural modulus.

[0042] In one embodiment, the composition has a dry modulus at 23 °C of at least 11 GPa and a dielectric constant Dk of less than or equal to 3.5 at 50% RH at frequencies of at least 1 GHz, the modulus corresponding to the flexural modulus.

[0043] In one embodiment, the composition has a dry modulus at 23 °C of at least 8 GPa and a dielectric constant Dk of less than or equal to 3.3 at 50% RH at a frequency of at least 1 GHz, and the modulus corresponds to the flexural modulus.

[0044] In one embodiment, the composition has a dry modulus at 23 °C of at least 10 GPa and a dielectric constant Dk of less than or equal to 3.3 at 50% RH at a frequency of at least 1 GHz, and the modulus corresponds to the flexural modulus.

[0045] In one embodiment, the composition has a dry modulus at 23 °C of at least 11 GPa and a dielectric constant Dk of less than or equal to 3.3 at 50% RH at a frequency of at least 1 GHz, and the modulus corresponds to the flexural modulus.

[0046] In one embodiment, the composition has a dry modulus at 23 °C of at least 8 GPa and a dielectric constant Dk of less than or equal to 3.2 at 50% RH at a frequency of at least 1 GHz, and the modulus corresponds to the flexural modulus.

[0047] In one embodiment, the composition has a dry modulus at 23 °C of at least 10 GPa and a dielectric constant Dk of less than or equal to 3.2 at 50% RH at a frequency of at least 1 GHz, and the modulus corresponds to the flexural modulus.

[0048] In one embodiment, the composition has a dry modulus at 23 °C of at least 11 GPa and a dielectric constant Dk of less than or equal to 3.2 at 50% RH at a frequency of at least 1 GHz, and the modulus corresponds to the flexural modulus.

[0049] In one embodiment, the composition has a dry modulus at 23 °C of at least 8 GPa and a dielectric constant Dk of less than or equal to 3.5 at 50% RH at a frequency up to 2.4 GHz, and the modulus corresponds to the flexural modulus.

[0050] In one embodiment, the composition has a dry modulus at 23 °C of at least 10 GPa and a dielectric constant Dk of less than or equal to 3.5 at 50% RH at a frequency up to 2.4 GHz, and the modulus corresponds to the flexural modulus.

[0051] In one embodiment, the composition has a dry modulus at 23 °C of at least 11 GPa and a dielectric constant Dk of less than or equal to 3.5 at 50% RH at a frequency up to 2.4 GHz, and the modulus corresponds to the flexural modulus.

[0052] In one embodiment, the composition has a dry modulus at 23 °C of at least 8 GPa and a dielectric constant Dk of less than or equal to 3.3 at 50% RH at frequencies up to 2.4 GHz, the modulus corresponding to the flexural modulus.

[0053] In one embodiment, the composition has a dry modulus at 23 °C of at least 10 GPa and a dielectric constant Dk of less than or equal to 3.3 at 50% RH at frequencies up to 2.4 GHz, the modulus corresponding to the flexural modulus.

[0054] In one embodiment, the composition has a dry modulus at 23 °C of at least 11 GPa and a dielectric constant Dk of less than or equal to 3.3 at 50% RH at frequencies up to 2.4 GHz, the modulus corresponding to the flexural modulus.

[0055] In one embodiment, the composition has a dry modulus at 23 °C of at least 8 GPa, and a dielectric constant Dk of less than or equal to 3.2 at 50% RH at frequencies up to 2.4 GHz, the modulus corresponding to the flexural modulus.

[0056] In one embodiment, the composition has a dry modulus at 23 °C of at least 10 GPa, and a dielectric constant Dk of less than or equal to 3.2 at 50% RH at frequencies up to 2.4 GHz, the modulus corresponding to the flexural modulus.

[0057] In one embodiment, the composition has a dry modulus at 23 °C of at least 11 GPa, and a dielectric constant Dk of less than or equal to 3.2 at 50% RH at frequencies up to 2.4 GHz, the modulus corresponding to the flexural modulus.

[0058] In one embodiment, the composition has a dry modulus at 23 °C of at least 8 GPa, and a dielectric constant Dk of less than or equal to 3.5 at 50% RH at frequencies of at least 1 GHz, the modulus corresponding to the tensile modulus.

[0059] In one embodiment, the composition has a dry modulus at 23 °C of at least 10 GPa, and a dielectric constant Dk of less than or equal to 3.5 at 50% RH at frequencies of at least 1 GHz, the modulus corresponding to the tensile modulus.

[0060] In one embodiment, the composition has a dry modulus at 23 °C of at least 11 GPa, and a dielectric constant Dk of less than or equal to 3.5 at 50% RH at frequencies of at least 1 GHz, the modulus corresponding to the tensile modulus.

[0061] In one embodiment, the composition has a dry modulus at 23 °C of at least 8 GPa, and a dielectric constant Dk of less than or equal to 3.3 at 50% RH at a frequency of at least 1 GHz, the modulus corresponding to the tensile modulus.

[0062] In one embodiment, the composition has a dry modulus at 23 °C of at least 10 GPa and a dielectric constant Dk of less than or equal to 3.3 at 50% RH at a frequency of at least 1 GHz, the modulus corresponding to the tensile modulus.

[0063] In one embodiment, the composition has a dry modulus at 23 °C of at least 11 GPa, and a dielectric constant Dk of less than or equal to 3.3 at 50% RH at a frequency of at least 1 GHz, the modulus corresponding to the tensile modulus.

[0064] In one embodiment, the composition has a dry modulus at 23 °C of at least 8 GPa, and a dielectric constant Dk of less than or equal to 3.2 at 50% RH at a frequency of at least 1 GHz, the modulus corresponding to the tensile modulus.

[0065] In one embodiment, the composition has a dry modulus at 23 °C of at least 10 GPa, and a dielectric constant Dk of less than or equal to 3.2 at 50% RH at a frequency of at least 1 GHz, the modulus corresponding to the tensile modulus.

[0066] In one embodiment, the composition has a dry modulus at 23 °C of at least 11 GPa, and a dielectric constant Dk of less than or equal to 3.2 at 50% RH at a frequency of at least 1 GHz, the modulus corresponding to the tensile modulus.

[0067] In one embodiment, the composition has a dry modulus at 23 °C of at least 8 GPa and a dielectric constant Dk of less than or equal to 3.5 at 50% RH at a frequency up to 2.4 GHz, the modulus corresponding to the tensile modulus.

[0068] In one embodiment, the composition has a dry modulus at 23 °C of at least 10 GPa and a dielectric constant Dk of less than or equal to 3.5 at 50% RH at a frequency up to 2.4 GHz, the modulus corresponding to the tensile modulus.

[0069] In one embodiment, the composition has a dry modulus at 23 °C of at least 11 GPa and a dielectric constant Dk of less than or equal to 3.5 at 50% RH at a frequency up to 2.4 GHz, the modulus corresponding to the tensile modulus.

[0070] In one embodiment, the composition has a dry modulus at 23 °C of at least 8 GPa and a dielectric constant Dk of less than or equal to 3.3 at 50% RH at frequencies up to 2.4 GHz, the modulus corresponding to the tensile modulus.

[0071] In one embodiment, the composition has a dry modulus at 23 °C of at least 10 GPa and a dielectric constant Dk of less than or equal to 3.3 at 50% RH at frequencies up to 2.4 GHz, the modulus corresponding to the tensile modulus.

[0072] In one embodiment, the composition has a dry modulus at 23 °C of at least 11 GPa and a dielectric constant Dk of less than or equal to 3.3 at 50% RH at frequencies up to 2.4 GHz, the modulus corresponding to the tensile modulus.

[0073] In one embodiment, the composition has a dry modulus at 23 °C of at least 8 GPa and a dielectric constant Dk of less than or equal to 3.2 at 50% RH at frequencies up to 2.4 GHz, the modulus corresponding to the tensile modulus.

[0074] In one embodiment, the composition has a dry modulus at 23 °C of at least 10 GPa and a dielectric constant Dk of less than or equal to 3.2 at 50% RH at frequencies up to 2.4 GHz, the modulus corresponding to the tensile modulus.

[0075] In one embodiment, the composition has a dry modulus at 23 °C of at least 11 GPa and a dielectric constant Dk of less than or equal to 3.2 at 50% RH at frequencies up to 2.4 GHz, the modulus corresponding to the tensile modulus.

[0076] Measurement of the dielectric loss (tanδ or tan(δ)) (or power factor (tanδ or tan(δ))) is used to determine the insulation state of the composition.

[0077] Advantageously, the dielectric loss (tanδ) of the composition is less than or equal to 0.01, which is measured on a dry sample according to ASTM D-2520-13 at 23 °C, at 50% RH, at frequencies of at least 1 GHz, particularly at frequencies up to 2.4 GHz.

[0078] The sample is then pre-dried, particularly at 80 °C for 5 days, and tested at 23 °C at 50% RH.

[0079] In one embodiment, the composition has a dry modulus and a dielectric constant Dk at 23 °C as defined above in the respective embodiments, and a dielectric loss (tan δ) less than or equal to 0.01, which is measured on a dry sample at 23 °C, at 50% RH, at the same frequency as the dielectric constant in the embodiment.

[0080] Regarding solid and hollow glass reinforcements

[0081] Solid glass reinforcement

[0082] Solid glass reinforcement is a glass fiber material having a solid (as opposed to hollow) structure, which can have any shape as long as it is solid.

[0083] The cross-section of these shapes can be circular or non-circular.

[0084] A shape with a circular cross-section is defined as a shape having a distance equal to the center of the shape at any point on its perimeter, thus representing a perfect or nearly perfect circle.

[0085] Therefore, any glass shape that does not have this perfect or nearly perfect circle is defined as a shape with a flat cross-section.

[0086] Non-limiting examples of flat cross-section shapes are flat shapes such as oval, egg-shaped or cocoon-shaped, star-shaped, flake-shaped, cross-shaped, polygonal and annular.

[0087] The solid glass shape can particularly be short solid glass fibers, which preferably have a length between 2 and 13 mm, preferably 3 to 8 mm, before using the composition.

[0088] The solid glass fibers can be:

[0089] - Having a circular cross-section with a diameter between 4 µm and 25 µm, preferably between 4 and 15 µm.

[0090] - Or having a non-circular cross-section with an L / D ratio between 2 and 8, particularly between 2 and 4 (where L represents the maximum dimension of the cross-section of the fiber and D represents the minimum dimension of the cross-section of the fiber). L and D can be measured by scanning electron microscopy (SEM).

[0091] Hollow glass reinforcement

[0092] Hollow glass reinforcement is a glass fiber material having a hollow (as opposed to solid) structure, which, like solid glass reinforcement, can have any shape as long as it is hollow.

[0093] The hollow glass shape can particularly be short hollow glass fibers, which preferably have a length between 2 and 13 mm, more preferably between 3 and 8 mm, before using the composition.

[0094] Hollow glass fibers mean glass fibers in which the hollow (or pore or window) inside the fiber is not necessarily concentric with the outer diameter of the fiber.

[0095] The hollow glass fibers can be:

[0096] - Having a circular cross-section with a diameter between 7.5 and 75 µm, preferably between 9 and 25 µm, more preferably between 10 and 12 µm.

[0097] Obviously, the diameter of the hollow (the term "hollow" can also be referred to as a pore or window) is not equal to the outer diameter of the hollow glass fiber.

[0098] Advantageously, the diameter of the hollow (or pore or window) is 10% to 80% of the outer diameter of the hollow fiber, especially 60% to 80%.

[0099] - Or having a non-circular cross-section with an L / D ratio between 2 and 8, particularly between 2 and 4 (where L represents the maximum dimension of the cross-section of the fiber and D represents the minimum dimension of the cross-section of the fiber). L and D can be measured by scanning electron microscopy (SEM).

[0100] The mixture of the solid and hollow glass reinforcements contains 5 wt% to 50 wt% of hollow glass beads, particularly 5 wt% to 35 wt% of hollow glass beads, based on the total of the solid and hollow glass reinforcements.

[0101] In one embodiment, the mixture of the solid and hollow glass reinforcements contains 10 wt% to 50 wt% of hollow glass beads, particularly 10 wt% to 35 wt% of hollow glass beads, based on the total of the solid and hollow glass reinforcements.

[0102] In one embodiment, the mixture of the solid and hollow glass reinforcements, in addition to hollow glass beads, further contains solid glass fibers selected from glass fibers with a circular cross-section, glass fibers with a flat cross-section, and mixtures thereof.

[0103] In one embodiment, the mixture of the solid and hollow glass reinforcements contains 5 wt% to 50 wt% of hollow glass beads, particularly 5 wt% to 35 wt% of hollow glass beads, based on the total of the solid and hollow glass reinforcements, and the hollow glass beads account for the entire proportion of the hollow reinforcement.

[0104] In this last embodiment, the mixture of solid and hollow glass reinforcing materials, in addition to the hollow glass beads that make up the entirety of the hollow reinforcing material, further comprises solid glass fibers selected from glass fibers with a circular cross-section, glass fibers with a flat cross-section, and mixtures thereof.

[0105] Advantageously, the mixture of glass reinforcing materials consists of 50% to 95% by weight of solid glass fibers and 5% to 50% by weight of hollow glass beads, particularly 65% to 95% by weight of solid glass fibers and 5% to 35% by weight of hollow glass beads.

[0106] Advantageously, the mixture of glass reinforcing materials consists of 50% to 90% by weight of solid glass fibers and 10% to 50% by weight of hollow glass beads, particularly 65% to 90% by weight of solid glass fibers and 10% to 35% by weight of hollow glass beads.

[0107] Advantageously, the solid glass fibers are glass fibers having a non-circular cross-section.

[0108] In one embodiment, the solid glass reinforcing material is a glass fiber having a Dk > 5 at a frequency of 1 MHz to 5 GHz and particularly a Dk > 5 and a Df < 0.005 at a frequency of 1 GHz.

[0109] Advantageously, the solid glass reinforcing material is a glass fiber having a non-circular cross-section and an elastic modulus of less than 76 GPa measured according to ASTM C1557-03.

[0110] Regarding an alloy composed of at least one polyamide and at least one polyolefin

[0111] Advantageously, the alloy consists of at least one polyamide and at least one polyolefin, and the weight ratio of polyamide / polyolefin is between 95 / 5 and 50 / 50.

[0112] Polyolefin:

[0113] The polyolefin of the composition can be a grafted (or functionalized) or non-grafted (or non-functionalized) polyolefin or a mixture thereof.

[0114] The grafted polyolefin can be a polymer of an α-olefin having reactive units (functional groups); such reactive units are acid, acid anhydride, or epoxy functional groups. By way of example, mention may be made of the aforementioned non-grafted polyolefins, which are however grafted, copolymerized, or trimerized with unsaturated epoxides such as glycidyl (meth)acrylate, or with carboxylic acids or the corresponding salts or esters such as (meth)acrylic acid (which can be fully or partially neutralized with a metal such as zinc, etc.), or even with carboxylic acid anhydrides such as maleic anhydride.

[0115] Advantageously, the grafted polyolefin is selected from: esters of unsaturated carboxylic acids, such as alkyl acrylates or alkyl methacrylates, preferably the alkyl group having 1 to 24 carbon atoms, and examples of alkyl acrylates or alkyl methacrylates are in particular methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate;

[0116] vinyl esters of saturated carboxylic acids, such as vinyl acetate or vinyl propionate.

[0117] Advantageously, the grafted polyolefin as defined above is based on polypropylene.

[0118] The non-grafted polyolefin is typically a homopolymer or copolymer of the following: α-olefins or dienes, such as ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene, 1-tetracosene, 1-hexacosene, 1-octacosene and 1-triacontene, preferably propylene or ethylene or dienes such as butadiene, which may be mixed with compatible and functional compatibilizers, such as polyethylene® mixed with maleated Lotader or maleated polyethylene, isoprene or 1,4-hexadiene.

[0119] In particular, the α-olefin homopolymers are selected from low density polyethylene (LDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE) and metallocene polyethylene;

[0120] In particular, the copolymers of α-olefins or dienes are selected from ethylene / α-olefin polymers, such as ethylene-propylene, ethylene-butene, ethylene-propylene-diene monomer, ethylene-octene, alone or mixed with polyethylene (PE);

[0121] Advantageously, the non-grafted polyolefin as defined above is based on polypropylene.

[0122] The polyolefin of the composition may also be crosslinked or non-crosslinked, or a mixture of at least one crosslinked and / or at least one non-crosslinked.

[0123] Crosslinked polyolefin

[0124] The polyolefin of the composition according to the present invention may be a non-crosslinked polyolefin and / or a crosslinked polyolefin, and the non-crosslinked and / or crosslinked polyolefin exists as a phase dispersed in a matrix formed by polyamide.

[0125] The crosslinked polyolefin is derived from the reaction of two or more products having reactive groups therebetween.

[0126] More particularly, when the polyolefin is a crosslinked polyolefin, it is obtained from at least one product (A) comprising an unsaturated epoxide and at least one product (B) comprising an unsaturated carboxylic anhydride.

[0127] Product (A) is advantageously a polymer comprising an unsaturated epoxide, which is introduced into the polymer by grafting or by copolymerization.

[0128] The unsaturated epoxide can be particularly selected from the following epoxides:

[0129] - aliphatic glycidyl esters and ethers, such as allyl glycidyl ether, vinyl glycidyl ether, glycidyl maleate and itaconate, glycidyl acrylate and methacrylate, and

[0130] - cycloaliphatic glycidyl esters and ethers, such as 2-cyclohexene-1-glycidyl ether, cyclohexene-4,5-diglycidyl carboxylate, cyclohexene-4-glycidyl carboxylate, 5-norbornene-2-methyl-2-glycidyl carboxylate and endo-cis-bicyclo(2,2,1)-5-heptene-2,3-diglycidyl dicarboxylate.

[0131] According to a first form, product (A) is a polyolefin grafted with an unsaturated epoxide. Polyolefin is understood to mean a homopolymer or copolymer comprising one or more olefin units such as ethylene, propylene or butene-1 units or any other α-olefin unit. As examples of polyolefins, mention may be made of:

[0132] - polyethylene, including low density polyethylene (LDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE) and very low density polyethylene (VLDPE); polypropylene; ethylene / propylene copolymer; elastomeric polyolefins such as ethylene-propylene (EPR or EPM) or ethylene-propylene-diene monomer (EPDM); or metallocene polyethylene obtained by single-site catalysis;

[0133] - styrene / ethylene-butene / styrene (SEBS) block copolymer; styrene / butadiene / styrene (SBS) block copolymer; styrene / isoprene / styrene (SIS) block copolymer; or styrene / ethylene-propylene / styrene block copolymer;

[0134] - copolymers of ethylene and a product selected from salts of unsaturated carboxylic acids, esters of unsaturated carboxylic acids and vinyl esters of saturated carboxylic acids. The polyolefin can particularly be a copolymer of ethylene and an alkyl (meth)acrylate or a copolymer of ethylene and vinyl acetate.

[0135] According to the second form, product (A) is a copolymer of an α-olefin and an unsaturated epoxide, and advantageously a copolymer of ethylene and an unsaturated epoxide. Advantageously, the amount of the unsaturated epoxide can be up to 15% by weight of the copolymer (A), and the amount of ethylene is at least 50% by weight of the copolymer (A).

[0136] Copolymers of ethylene, vinyl esters of saturated carboxylic acids and unsaturated epoxides, and copolymers of ethylene, alkyl (meth)acrylates and unsaturated epoxides can be more particularly cited. Preferably, the alkyl group of the (meth)acrylate contains 2 to 10 carbon atoms. Examples of alkyl acrylates or alkyl methacrylates that can be used include methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and 2-ethylhexyl acrylate.

[0137] According to an advantageous embodiment of the present invention, product (A) is a copolymer of ethylene, methyl acrylate and glycidyl methacrylate or a copolymer of ethylene, n-butyl acrylate and glycidyl methacrylate. In particular, the product sold by ARKEMA under the name LOTADER® AX8900 can be used.

[0138] According to another form of the present invention, product (A) is a product having two epoxide functional groups, such as diglycidyl ether of bisphenol A (DGEBA).

[0139] Product (B) is advantageously a polymer containing an unsaturated carboxylic anhydride, which is introduced into the polymer by grafting or by copolymerization.

[0140] Examples of unsaturated dicarboxylic anhydrides that can be used as components of product (B) include maleic anhydride, itaconic anhydride, citraconic anhydride, and tetrahydrophthalic anhydride.

[0141] According to the first form, product (B) is a polyolefin grafted with an unsaturated carboxylic anhydride. As described above, the polyolefin is a homopolymer or copolymer containing one or more olefin units such as ethylene, propylene or butene-1 units or any other α-olefin units. The polyolefin can be particularly selected from the examples of polyolefins listed above for product (A) when product (A) is a polyolefin grafted with an unsaturated epoxide.

[0142] According to the second form, product (B) is a copolymer of an α-olefin and an unsaturated carboxylic anhydride, and advantageously a copolymer of ethylene and an unsaturated carboxylic anhydride. Advantageously, the amount of the unsaturated carboxylic anhydride can be up to 15% by weight of the copolymer (B), and the amount of ethylene is at least 50% by weight of the copolymer (B).

[0143] Copolymers of ethylene, vinyl esters of saturated carboxylic acids and unsaturated carboxylic anhydrides, and copolymers of ethylene, (meth)acrylic alkyl esters and unsaturated carboxylic anhydrides can be specifically mentioned. Preferably, the alkyl group of the (meth)acrylate contains 2 to 10 carbon atoms. The alkyl acrylate or alkyl methacrylate can be selected from those listed above for product (A).

[0144] According to an advantageous form of the invention, product (B) is a copolymer of ethylene, (meth)acrylic alkyl ester and unsaturated carboxylic anhydride. Preferably, product (B) is a copolymer of ethylene, ethyl acrylate and maleic anhydride or a copolymer of ethylene, butyl acrylate and maleic anhydride. In particular, products sold by ARKEMA under the names LOTADER® 4700 and LOTADER® 3410 can be used.

[0145] It is not outside the scope of the invention if part of the maleic anhydride of product (B) according to the first and second forms just described is partially hydrolyzed.

[0146] Advantageously, the weight contents of product (A) and product (B), denoted by [A] and [B] respectively, are such that the ratio [B] / [A] is between 3 and 14, and advantageously between 4 and 9.

[0147] In the composition according to the invention, the crosslinked polyolefin can also be obtained from product (A), (B) as described above and at least one product (C) which contains an unsaturated carboxylic acid or an α,ω - amino carboxylic acid.

[0148] Product (C) is advantageously a polymer containing an unsaturated carboxylic acid or an α,ω - amino carboxylic acid, and any of these acids is introduced into the polymer by copolymerization.

[0149] Examples of unsaturated carboxylic acids that can be used as components of product (C) include acrylic acid, methacrylic acid, and the carboxylic anhydrides mentioned above as components of product (B), which are completely hydrolyzed.

[0150] Examples of α,ω - amino carboxylic acids suitable for use as components of product (C) include 6 - aminohexanoic acid, 11 - aminoundecanoic acid, and 12 - aminododecanoic acid.

[0151] Product (C) can be a copolymer of an α - olefin and an unsaturated carboxylic acid, and advantageously a copolymer of ethylene and an unsaturated carboxylic acid. The completely hydrolyzed copolymer of product (B) can be specifically mentioned.

[0152] According to an advantageous form of the invention, the product (C) is a copolymer of ethylene and (meth)acrylic acid or a copolymer of ethylene, an alkyl (meth)acrylate and (meth)acrylic acid. The amount of (meth)acrylic acid can be up to 10% by weight, and preferably 0.5% to 5% by weight, of the copolymer (C). The amount of alkyl (meth)acrylate is generally between 5% and 40% by weight of the copolymer (C).

[0153] Advantageously, the product (C) is a copolymer of ethylene, butyl acrylate and acrylic acid, such as Escor™ 5000 from ExxonMobil.

[0154] Preferably, the product (C) is a copolymer of ethylene, butyl acrylate and acrylic acid. In particular, the product sold by BASF under the name LUCALENE® 3110 can be used.

[0155] Of course, the crosslinked polyolefin dispersed phase can be prepared by reacting one or more products (A) with one or more products (B) and, if appropriate, with one or several products (C).

[0156] As already described in WO 2011 / 015790, catalysts can be used to accelerate the reaction between the reactive functional groups of products (A) and (B). Examples of catalysts are given in that document and they can be used in a weight ratio of 0.1% to 3%, advantageously 0.5% to 1%, based on the total weight of products (A), (B) and, if appropriate, (C).

[0157] Advantageously, the weight contents of the products (A), (B) and (C), denoted by [A], [B] and [C] respectively, are such that the ratio [B] / ([A]+[C]) is between 1.5 and 8 and the weight contents of products (A) and (B) are such that [C]≤[A].

[0158] Advantageously, the ratio [B] / ([A]+[C]) is between 2 and 7.

[0159] Non-crosslinked polyolefin

[0160] The composition according to the invention can comprise at least one non-crosslinked polyolefin in the form of a phase dispersed in a matrix formed by a semi-crystalline polyamide.

[0161] Non-crosslinked polyolefins are understood to mean homopolymers or copolymers comprising one or more olefin units such as ethylene, propylene or butene-1 units or any other α-olefin unit as defined above.

[0162] Advantageously, the composition comprises at least one crosslinked polyolefin as defined above and at least one non-crosslinked polyolefin as defined above.

[0163] In one embodiment, the alloy consists of at least one polyamide and a mixture of a polypropylene-based graft polyolefin and a polypropylene-based non-grafted polyolefin.

[0164] Polyamide:

[0165] The at least one polyamide is selected from semi-crystalline polyamides, amorphous polyamides, and mixtures thereof.

[0166] Advantageously, the at least one polyamide is selected from amorphous single polyamides, semi-crystalline polyamides, and mixtures of two semi-crystalline polyamides.

[0167] In the context of the present invention, a semi-crystalline copolyamide means a polyamide that has a glass transition temperature in DSC according to ISO standard 11357-2:2013 and a melting temperature (Tm) in DSC according to ISO standard 11357-3:2013, and a crystallization enthalpy in DSC measured according to ISO standard 11357-3:2013 during a cooling step at a rate of 20 K / min that is greater than 30 J / g, preferably greater than 40 J / g.

[0168] In the context of the present invention, an amorphous polyamide means a polyamide that has only a glass transition temperature in DSC according to ISO standard 11357-2:2013 (and not a melting temperature (Tm)), or a polyamide that has a very low crystallinity, and whose glass transition temperature and melting point in DSC according to ISO standard 11357-2:2013 are such that the crystallization enthalpy in differential scanning calorimetry DSC during a cooling step at a rate of 20 K / min measured according to ISO standard 11357-3:2013 is less than 30 J / g, particularly less than 20 J / g, preferably less than 15 J / g.

[0169] The nomenclature used to define polyamides is described in ISO standard 1874-1:2011 "Plastiques -- Matériaux polyamides (PA) pour moulage et extrusion -- Partie 1: Designation", particularly on page 3 (Tables 1 and 2) and is well known to those skilled in the art.

[0170] In a first variant, the alloy consists of a single polyamide that is an amorphous polyamide and at least one polyolefin.

[0171] Amorphous polyamide:

[0172] The amorphous polyamide can be a polyamide of the formula A / XY, where:

[0173] A is an aliphatic repeating unit obtained by polycondensation of:

[0174] at least one C5 to C 18 and preferably C6 to C 12 and more preferably C 10 to C 12 amino acid, or

[0175] at least one C5 to C 18 and preferably C6 to C 12 and more preferably C 10 to C 12 lactam, or

[0176] at least one C4-C 36 and preferably C6-C 18 and preferably C6-C 12 and more preferably C 10 -C 12 aliphatic diamine Ca and at least one C4-C 36 and preferably C6-C 18 and preferably C6-C 12 and more preferably C8-C 12 dicarboxylic acid Cb;

[0177] XY is an aliphatic repeating unit obtained by polycondensation of:

[0178] at least one alicyclic diamine, or at least one straight-chain or branched aliphatic diamine X and

[0179] at least one aromatic dicarboxylic acid or at least one aliphatic dicarboxylic acid Y.

[0180] The amino acids may be particularly 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, especially 11-aminoundecanoic acid.

[0181] The lactams may be selected from pyrrolidone, 2-piperidone, caprolactam, enantholactam, caprylolactam, pelargolactam, caprindolactam, undecalactam and laurolactam, especially laurolactam.

[0182] The C4-C 36The aliphatic diamine Ca is straight-chain or branched and is particularly selected from butanediamine, 1,5-pentamethylenediamine, 2-methyl-1,5-pentanediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 2-methyl-1,8-octamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,10-decanediamine, 1,11-undecanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, 1,18-octadecanediamine, 1,20-icosanediamine, 1,22-docosanediamine, and fatty acid dimers.

[0183] The C6-C 18 The aliphatic diamine Ca is straight-chain or branched and is particularly selected from 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 2-methyl-1,8-octamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,10-decanediamine, 1,11-undecanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, 1,18-octadecanediamine.

[0184] The C6-C 12 The aliphatic diamine Ca is straight-chain or branched and is particularly selected from 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 2-methyl-1,8-octamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,10-decanediamine, 1,11-undecanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,12-dodecanediamine.

[0185] The C 10 -C 12 The aliphatic diamine Ca is straight-chain or branched and is particularly selected from 1,10-decanediamine, 1,11-undecanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,12-dodecanediamine.

[0186] The C4-C 36 , preferably C6-C 18 , preferably C6-C 12 , more preferably C8-C 12 dicarboxylic acid Cb;

[0187] The C4-C36 dicarboxylic acid Cb is aliphatic and straight-chain and is particularly selected from succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and docosanedioic acid.

[0188] The C6-C 18 The dicarboxylic acid Cb is aliphatic and straight-chain and is particularly selected from adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, and octadecanedioic acid.

[0189] The C6-C 12 The dicarboxylic acid Cb is aliphatic and straight-chain and is particularly selected from adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid.

[0190] The C8-C 12 The dicarboxylic acid Cb is aliphatic and straight-chain and is particularly selected from suberic acid, azelaic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid.

[0191] In the aliphatic repeating unit XY, the diamine X can particularly be an alicyclic diamine, which 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 bis(cyclohexylamine) (PACP), isophorone diamine, piperazine, amino-ethyl piperazine.

[0192] It may also include the following carbon skeletons: norbornylmethane, cyclohexylmethane, dicyclohexylpropane, bis(methylcyclohexyl), bis(methylcyclohexyl)propane. A non-exhaustive list of these alicyclic diamines is given in the publication "Cycloaliphatic Amines" (Encyclopaedia of Chemical Technology, Kirk-Othmer, 4th Edition (1992), pp. 386–405).

[0193] In the aliphatic repeating unit XY, the diamine X can particularly be a straight-chain or branched aliphatic diamine and is selected from those defined above for diamine Ca.

[0194] In the aliphatic repeating unit XY, the diacid Y can be an aromatic dicarboxylic acid selected from terephthalic acid (represented as T), isophthalic acid (represented as I), and naphthalenedicarboxylic acid.

[0195] In the aliphatic repeating unit XY, the diacid Y can be an aliphatic dicarboxylic acid Y and is selected from those defined above for the diacid Cb.

[0196] Obviously, the unit XY is different from the diamine unit Ca.diacid Cb.

[0197] Advantageously, A is an aliphatic repeating unit obtained by polycondensation of: at least one C5 to C 18 , preferably C6 to C 12 , more preferably C 10 to C 12 amino acid, or

[0198] at least one C5 to C 18 , preferably C6 to C 12 , more preferably C 10 to C 12 lactam.

[0199] Advantageously, XY is an aliphatic repeating unit obtained by polycondensation of at least one cycloaliphatic diamine and at least one aromatic dicarboxylic acid or at least one aliphatic dicarboxylic acid Y.

[0200] Advantageously, A is an aliphatic repeating unit obtained by polycondensation of: at least one C5 to C 18 , preferably C6 to C 12 , more preferably C 10 to C 12 amino acid, or

[0201] at least one C5 to C 18 , preferably C6 to C 12 , more preferably C 10 to C 12 lactam, and XY is an aliphatic repeating unit obtained by polycondensation of at least one cycloaliphatic diamine and at least one aromatic dicarboxylic acid or at least one aliphatic dicarboxylic acid Y.

[0202] Advantageously, A is an aliphatic repeating unit obtained by polycondensation of: at least one C 10 to C 12 amino acid or at least one C 10 to C 12 lactam, and XY is an aliphatic repeating unit obtained by polycondensation of at least one cycloaliphatic diamine and at least one aromatic dicarboxylic acid or at least one aliphatic dicarboxylic acid Y

[0203] Advantageously, the amorphous polyamide is selected from 11 / B10, 12 / B10, 11 / BI / BT, 11 / BI, in particular 11 / B10.

[0204] Advantageously, A is an aliphatic repeating unit obtained by polycondensation of: at least one C 10 to C 12 amino acid or at least one C 10 to C 12 lactam, and XY is an aliphatic repeating unit obtained by polycondensation of at least one cycloaliphatic diamine and at least one aromatic dicarboxylic acid.

[0205] Advantageously, the amorphous polyamide is selected from 11 / BI / BT and 11 / BI.

[0206] Advantageously, A is an aliphatic repeating unit obtained by polycondensation of: at least one C 10 to C 12 amino acid or at least one C 10 to C 12 lactam, and XY is an aliphatic repeating unit obtained by polycondensation of at least one cycloaliphatic diamine and at least one aliphatic dicarboxylic acid Y.

[0207] Advantageously, the amorphous polyamide is selected from 11 / B10, 12 / B10, in particular 11 / B10.

[0208] Advantageously, the alloy consists of a single polyamide which is an amorphous polyamide and a mixture of a polypropylene-based graft polyolefin and a polypropylene-based non-grafted polyolefin.

[0209] In a second variant, the alloy consists of a single semi-crystalline polyamide or a mixture of two semi-crystalline polyamides and at least one polyolefin.

[0210] The polyolefin is as defined above.

[0211] Semi-crystalline polyamide:

[0212] The semi-crystalline polyamide may be selected from aliphatic polyamides, in particular long-chain polyamides, aryl-aliphatic polyamides and semi-aromatic polyamides.

[0213] The expression "aliphatic polyamide" means a homopolyamide or a copolyamide. It is understood that it may be a mixture of aliphatic polyamides.

[0214] The expression "long-chain" means that the average number of carbon atoms per nitrogen atom is greater than 8, in particular from 9 to 18.

[0215] In one embodiment, the polyamide mixture is a mixture of an aliphatic polyamide, in particular a long-chain polyamide, and an aryl-aliphatic polyamide.

[0216] Aliphatic polyamides can be obtained by polycondensation of lactams, which may be selected from pyrrolidone, 2-piperidone, caprolactam, enantholactam, caprylolactam, pelargonolactam, caprilactam, undecalactam and lauryllactam, especially lauryllactam.

[0217] Aliphatic polyamides can be obtained by polycondensation of amino acids, which may be selected from 9-aminononanoic acid, 10-aminodecanoic acid, 10-aminoundecanoic acid, 12-aminododecanoic acid and 11-aminoundecanoic acid and their derivatives, especially N-heptyl-11-aminoundecanoic acid, especially 11-aminoundecanoic acid.

[0218] Aliphatic polyamides can be obtained by polycondensation of units X1Y1, where X1 is a diamine and Y is a dicarboxylic acid.

[0219] X1 can be a straight-chain or branched C5-C18 aliphatic diamine and may particularly be selected from 1,5-pentamethylenediamine, 2-methyl-1,5-pentanediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 2-methyl-1,8-octanediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,12-dodecamethylenediamine, 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,16-hexadecamethylenediamine and 1,18-octadecamethylenediamine.

[0220] Advantageously, the diamine X1 used is C6-C12, particularly selected from butanediamine, pentanediamine, 2-methyl-1,5-pentanediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 2-methyl-1,8-octanediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,12-dodecamethylenediamine.

[0221] Advantageously, the diamine X1 used is C10 to C12, particularly selected from 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 2-butyl-2-ethyl-1,5-pentanediamine and 1,12-dodecamethylenediamine,

[0222] Y1 can be a C6-C18 aliphatic dicarboxylic acid, especially C6-C12, in particular C10-C12.

[0223] The C6 to C18 aliphatic dicarboxylic acid Y1 can be selected from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid.

[0224] The C6 to C12 aliphatic dicarboxylic acid Y1 can be selected from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid.

[0225] The C10 to C12 aliphatic dicarboxylic acid Y1 can be selected from sebacic acid, undecanedioic acid, dodecanedioic acid.

[0226] Advantageously, the aliphatic polyamide is selected from PA6, PA66, PA610, PA612, PA1010, PA1012, PA1212, PA11 and PA12, especially PA1010, PA1012, PA1212, PA11 and PA12.

[0227] The expression "aryl-aliphatic polyamide" means a polyamide obtained by polycondensation of the units X2Y1, where X2 represents an aromatic diamine and Y1 represents an aliphatic dicarboxylic acid, as defined above.

[0228] The aromatic diamine X2 can be selected from m-xylene diamine (MXD) and p-xylene diamine (PXD).

[0229] Advantageously, the aryl-aliphatic polyamide is selected from MXD6, MXD10, MXD12.

[0230] Advantageously, the aryl-aliphatic polyamide is selected from MXD10, MXD12.

[0231] Advantageously, the mixture of the two semi-crystalline polyamides is a mixture of an aliphatic polyamide and an aryl-aliphatic polyamide.

[0232] Advantageously, the mixture of the two semi-crystalline polyamides is a mixture of an aliphatic polyamide selected from PA6, PA66, PA610, PA612, PA1010, PA1012, PA1212, PA11 and PA12, especially PA1010, PA1012, PA1212, PA11 and PA12, and an aryl-aliphatic polyamide selected from MXD6, MXD10 and MXD12.

[0233] Advantageously, the mixture of the two semi-crystalline polyamides is a mixture of an aliphatic polyamide selected from PA1010, PA1012, PA1212, PA11 and PA12 and an aryl-aliphatic polyamide selected from MXD10, MXD12.

[0234] The expression "semi-aromatic polyamide" particularly means a semi-aromatic polyamide having the formula as described in EP1505099, in particular a semi-aromatic polyamide of formula B / ZT, where B is selected from units obtained by polycondensation of amino acids as defined above, units obtained by polycondensation of lactams as defined above, and units corresponding to formula X2Y2, where X2 and Y2 are as defined above;

[0235] ZT represents a unit obtained by polycondensation of Cx diamine and terephthalic acid, where x represents the number of carbon atoms of Cx diamine, x is between 4 and 36, advantageously between 6 and 18, advantageously between 6 and 12, advantageously between 10 and 12, in particular polyamides having the formula A / 6T, A / 9T, A / 10T or A / 11T, A as defined above, in particular polyamides PA 6 / 6T, PA 66 / 6T, PA 6I / 6T, PA 11 / 9T, PA 11 / 10T, PA 11 / 12T, PA 12 / 9T, PA 12 / 10T, PA 12 / 12T, PA MPMDT / 6T, PA MXDT / 6T, PA 11 / 6T / 10T, PA MXDT / 10T, PA MPMDT / 10T, PA BACT / 10T, PA BACT / 6T, PA BACT / 10T / 6T, PA 11 / BACT / 10T, PA 11 / MPMDT / 10T, and PA 11 / MXDT / 10T, and block copolymers, in particular polyamide / polyether (PEBA).

[0236] T corresponds to terephthalic acid, MXD corresponds to m-xylenediamine, MPMD corresponds to methylpentamethylenediamine and BAC corresponds to bis(aminomethyl)cyclohexane (1,3 BAC and / or 1,4 BAC).

[0237] Advantageously, the semi-aromatic polyamide is selected from PA11 / 9T, PA11 / 10T, PA 11 / 12T, PA12 / 9T, PA12 / 10T, PA12 / 12T.

[0238] Advantageously, the at least one polyamide is selected from: a single amorphous polyamide, an aryl-aliphatic polyamide, a mixture of an aliphatic polyamide, particularly a long-chain polyamide and an aryl-aliphatic polyamide, and a mixture of an aliphatic polyamide, particularly a long-chain polyamide and a semi-aromatic polyamide.

[0239] Advantageously, the alloy consists of a mixture of two semi-crystalline polyamides and a mixture of a grafted polyolefin based on polypropylene and a non-grafted polyolefin based on polypropylene.

[0240] In one embodiment, the present invention relates to the use as defined above, wherein the composition contains an additive.

[0241] Additive

[0242] The additives may be present up to 2% by weight, in particular 1% to 2% by weight, based on the total weight of the composition.

[0243] The additives may be selected from catalysts, antioxidants, heat stabilizers, UV stabilizers, light stabilizers, lubricants, flame retardants, nucleating agents, chain extenders and colorants.

[0244] The term "catalyst" means a polycondensation catalyst, such as an inorganic or organic acid.

[0245] Advantageously, the weight ratio of the catalyst is from about 50 ppm to about 5000 ppm, in particular about 100 to about 3000 ppm, based on the total weight of the composition.

[0246] Advantageously, the catalyst is selected from phosphoric acid (H3PO4), phosphorous acid (H3PO3), hypophosphorous acid (H3PO2) or mixtures thereof.

[0247] The antioxidant may in particular be an antioxidant based on a copper complex in an amount of 0.05% to 5% by weight, preferably 0.05% to 1% by weight, preferably 0.1% to 1%.

[0248] The expression copper complex particularly means a complex between a monovalent or divalent copper salt of an organic or inorganic acid and an organic ligand.

[0249] Advantageously, the copper salt is selected from copper (Cu(II)) salts of hydrogen halides, copper (Cu(I)) salts of hydrogen halides and salts of aliphatic carboxylic acids.

[0250] In particular, the copper salt is selected from CuCl, CuBr, CuI, CuCN, CuCl2, Cu(OAc)2, cuprous stearate.

[0251] Copper complexes are particularly described in US3505285.

[0252] The copper-based complex may further comprise a ligand selected from: phosphines, in particular triphenylphosphine, mercaptobenzimidazole, EDTA, acetylacetonate, glycine, ethylenediamine, oxalate, diethylenediamine, triethylenetetramine, pyridine, tetrabromobiphenyl-A, derivatives of tetraphenyl-A, such as epoxy derivatives, and derivatives of chlorodimethanedibenzo(a,e)cyclooctene and mixtures thereof, diphosphines and bipyridine or mixtures thereof, in particular triphenylphosphine and / or mercaptobenzimidazole.

[0253] Phosphine means an alkylphosphine, such as tributylphosphine or an arylphosphine, such as triphenylphosphine (TPP).

[0254] Advantageously, the ligand is triphenylphosphine.

[0255] Examples of complexes and how to prepare them are described in Patent CA 02347258.

[0256] Advantageously, the amount of copper in the composition of the present invention is 10 ppm to 1000 ppm by weight, particularly 20 ppm to 70 ppm, and particularly 50 ppm to 150 ppm, based on the total weight of the composition.

[0257] Advantageously, the copper-based complex further comprises a halogenated organic compound.

[0258] The halogenated organic compound can be any halogenated organic compound.

[0259] Advantageously, the halogenated organic compound is a bromine-based compound and / or an aromatic compound.

[0260] Advantageously, the aromatic compound is particularly selected from decabromodiphenyl, decabromodiphenyl ether, bromo- or chlorostyrene oligomers, polydibromostyrene.

[0261] Advantageously, the halogenated organic compound is a bromine-based compound.

[0262] The halogenated organic compound is added to the composition in a proportion of 50 to 30,000 ppm, particularly 100 to 10,000, and particularly 500 to 1500 ppm, based on the weight of the halogen relative to the total weight of the composition.

[0263] Advantageously, the copper:halogen molar ratio is 1:1 to 1:3000, particularly 1:2 to 1:100.

[0264] Particularly, the ratio is 1:1.5 to 1:15.

[0265] Advantageously, an antioxidant of the copper-based complex.

[0266] The heat stabilizer can be an organic stabilizer or more generally a combination of organic stabilizers, such as a primary antioxidant of the phenolic type (e.g., irganox 245 or type 1098 or 1010 from Ciba), or a secondary antioxidant of the phosphite type.

[0267] The UV stabilizer can be a HALS, which means a hindered amine light stabilizer or an anti-UV agent (e.g., Tinuvin 312 from Ciba).

[0268] The light stabilizer can be a hindered amine (e.g., Tinuvin 770 from Ciba), a phenolic or a phosphorus-based stabilizer.

[0269] The lubricant can be a lubricant of the fatty acid type, such as stearic acid.

[0270] The flame retardant can be a halogen-free flame retardant as described in US 2008 / 0274355, and in particular a phosphorus-based flame retardant, such as metal salts selected from: metal salts of hypophosphorous acid, in particular dialkyl hypophosphites, in particular aluminum diethylphosphinate or aluminum diethylphosphonate, metal salts of secondary phosphonic acid, mixtures of aluminum hypophosphite flame retardants and nitrogen synergists or mixtures of aluminum hypophosphite flame retardants and phosphorus synergists, polymers containing at least one metal salt of hypophosphorous acid, in particular based on ammonium, such as ammonium polyphosphate, ammonium sulfamate or ammonium pentaborate, or based on melamine, such as melamine, melamine salts, melamine pyrophosphate and melamine cyanurate, or based on cyanuric acid, or polymers containing at least one metal salt of secondary phosphonic acid or red phosphorus, antimony oxide, zinc oxide, iron oxide, magnesium oxide or metal borates such as zinc borate, or phosphazenes (phosphazines), phosphamines or phosphonitrilic oxides or mixtures thereof. It can also be a halogenated flame retardant, such as brominated or polybrominated polystyrene, brominated polycarbonate or brominated phenol.

[0271] The nucleating agent can be silica, alumina, clay or talc, in particular talc.

[0272] Examples of suitable chain limiters are monoamines, monocarboxylic acids, diamines, triamines, dicarboxylic acids, tricarboxylic acids, tetraamines, tetracarboxylic acids and oligomeric amines or oligomeric carboxylic acids each having 5 to 8 amino or carboxyl groups in each case, and in particular dicarboxylic acids, tricarboxylic acids or mixtures of dicarboxylic acids and tricarboxylic acids. For example, dodecanedioic acid in the form of a dicarboxylic acid and trimellitic acid as a tricarboxylic acid can be used.

[0273] In another embodiment, the present invention relates to the use as defined above, wherein the composition comprises at least one prepolymer, in particular a monofunctional NH2, in particular based on PA11.

[0274] Advantageously, the composition comprises a single prepolymer.

[0275] Prepolymer

[0276] The prepolymer can be present up to 11% by weight, in particular 0.1% to 11% by weight based on the total weight of the composition.

[0277] The prepolymer is different from the nucleating agent used as an additive.

[0278] The term "prepolymer" refers to oligomers of polyamides whose number average molecular weight must be lower than the number average molecular weight of the polyamide used in the composition, in particular the prepolymer has a number average molecular weight of 1000 - 15000 g / mol, in particular 1000 - 10000 g / mol.

[0279] The prepolymer may be selected from aliphatic, linear or branched polyamide oligomers, cycloaliphatic polyamide oligomers, semi-aromatic polyamide oligomers, aromatic polyamide oligomers, aliphatic, linear or branched, cycloaliphatic, semi-aromatic and aromatic polyamides, which have the same definitions as above.

[0280] Thus, the prepolymer or oligomer results from the condensation of:

[0281] - at least one lactam, or

[0282] - at least one amino acid, or

[0283] - at least one diamine and at least one dicarboxylic acid, or a mixture thereof.

[0284] Thus, the prepolymer or oligomer does not correspond to the condensation of a diamine with a lactam or an amino acid.

[0285] The prepolymer may also be a copolyamide oligomer or a mixture of a polyamide and a copolyamide oligomer.

[0286] For example, the prepolymer is a monofunctional NH2, monofunctional CO2H or bifunctional CO2H or NH2.

[0287] Thus, the prepolymer may be a monofunctional or bifunctional acid or amine, i.e., when it is monofunctional (in which case the other end is non-functional, especially CH3), it has a single terminal amine or acid functional group, or when it is bifunctional, it has two terminal amine functional groups or two terminal acid functional groups.

[0288] Advantageously, the prepolymer is monofunctional, preferably NH2 or CO2H.

[0289] It may also be non-functional at both ends, especially di-CH3.

[0290] In one embodiment, the present invention relates to the use as defined above, wherein the composition comprises:

[0291] 30% to 70% by weight, especially 35% to 60% by weight and more especially 40% to 50% by weight of an alloy composed of at least one polyamide and at least one polyolefin as defined above, with a polyamide / polyolefin ratio of 95 / 5 to 50 / 50;

[0292] 30% to 70% by weight, especially 40% to 65% by weight and more especially 50% to 60% by weight of a mixture of solid and hollow glass reinforcing materials as defined above; and

[0293] 0% to 11% by weight of at least one prepolymer, especially 0.1% to 11%;

[0294] 0% to 5% filler and

[0295] 0% to 2% by weight, preferably 1% to 2% by weight, of an additive,

[0296] The sum of the proportions of each component of the composition is equal to 100%.

[0297] In another embodiment, the present invention relates to the use as defined above, wherein the composition consists of:

[0298] 30% to 70% by weight, especially 35% to 60% by weight and more especially 40% to 50% by weight, of an alloy as defined above consisting of at least one polyamide and at least one polyolefin, with a polyamide / polyolefin ratio of 95 / 5 to 50 / 50;

[0299] 30% to 70% by weight, especially 40% to 65% by weight and more especially 50% to 60% by weight, of a mixture of solid and hollow glass reinforcing materials as defined above; and

[0300] 0% to 11% by weight of at least one prepolymer, especially 0.1% to 11%;

[0301] 0% to 5% filler and

[0302] 0% to 2% by weight, preferably 1% to 2% by weight, of an additive,

[0303] The sum of the proportions of each component of the composition is equal to 100%.

[0304] In one embodiment, the present invention relates to the use as defined above, wherein the composition comprises:

[0305] 30% to 50% by weight, especially 35% to 50% by weight and more especially 40% to 50% by weight, of an alloy as defined above consisting of at least one polyamide and at least one polyolefin, with a polyamide / polyolefin ratio of 95 / 5 to 50 / 50;

[0306] 50% to 70% by weight, especially 50% to 65% by weight and more especially 50% to 60% by weight, of a mixture of solid and hollow glass reinforcing materials as defined above; and

[0307] 0% to 11% by weight of at least one prepolymer, especially 0.1% to 11%;

[0308] 0% to 5% filler and

[0309] 0% to 2% by weight, preferably 1% to 2% by weight, of an additive,

[0310] The sum of the proportions of each component of the composition is equal to 100%.

[0311] In yet another embodiment, the invention relates to the use as defined above, wherein the composition consists of:

[0312] 30% to 50% by weight, particularly 35% to 50% by weight and more particularly 40% to 50% by weight of an alloy as defined above consisting of at least one polyamide and at least one polyolefin, with a polyamide / polyolefin ratio of 95 / 5 to 50 / 50;

[0313] 50% to 70% by weight, particularly 50% to 65% by weight and more particularly 50% to 60% by weight of a mixture of solid and hollow glass reinforcing materials as defined above; and

[0314] 0% to 11% by weight of at least one prepolymer, particularly 0.1% to 11%;

[0315] 0% to 5% of a filler and

[0316] 0% to 2% by weight, preferably 1% to 2% by weight, of an additive,

[0317] The sum of the proportions of each component of the composition is equal to 100%.

[0318] According to another aspect, the invention relates to a composition which can be used in particular for injection moulding, the composition comprising:

[0319] 30% to 70% by weight, particularly 35% to 60% by weight and more particularly 40% to 50% by weight of an alloy as defined above consisting of at least one polyamide and at least one polyolefin, with a polyamide / polyolefin ratio of 95 / 5 to 50 / 50;

[0320] 30% to 70% by weight, particularly 40% to 65% by weight and more particularly 50% to 60% by weight of a mixture of solid and hollow glass reinforcing materials as defined above; and

[0321] 0% to 11% by weight of at least one prepolymer, particularly 0.1% to 11%;

[0322] 0% to 5% of a filler and

[0323] 0% to 2% by weight, preferably 1% to 2% by weight, of an additive,

[0324] The sum of the proportions of each component of the composition is equal to 100%.

[0325] Advantageously, the composition, particularly for injection molding, consists of:

[0326] 30% to 70% by weight, particularly 35% to 60% by weight and more particularly 40% to 50% by weight of an alloy as defined above, consisting of at least one polyamide and at least one polyolefin, with a polyamide / polyolefin ratio of 95 / 5 to 50 / 50;

[0327] 30% to 70% by weight, particularly 40% to 65% by weight and more particularly 50% to 60% by weight of a mixture of solid and hollow glass reinforcing materials as defined above; and

[0328] 0% to 11% by weight of at least one prepolymer, particularly 0.1% to 11%;

[0329] 0% to 5% of fillers and

[0330] 0% to 2% by weight, 1% to 2% by weight of additives,

[0331] The sum of the proportions of each component of the composition is equal to 100%.

[0332] In one embodiment, the composition, particularly for injection molding, comprises:

[0333] 30% to 50% by weight, particularly 35% to 50% by weight and more particularly 40% to 50% by weight of an alloy as defined above, consisting of at least one polyamide and at least one polyolefin, with a polyamide / polyolefin ratio of 95 / 5 to 50 / 50;

[0334] 50% to 70% by weight, particularly 50% to 65% by weight and more particularly 50% to 60% by weight of a mixture of solid and hollow glass reinforcing materials as defined above; and

[0335] 0% to 11% by weight of at least one prepolymer, particularly 0.1% to 11%;

[0336] 0% to 5% of fillers and

[0337] 0% to 2% by weight, preferably 1% to 2% by weight of additives,

[0338] The sum of the proportions of each component of the composition is equal to 100%.

[0339] In another embodiment, the composition, particularly for injection molding, consists of:

[0340] An alloy consisting of at least one polyamide and at least one polyolefin as defined above, in an amount of 30% to 50% by weight, particularly 35% to 50% by weight and more particularly 40% to 50% by weight, with a polyamide / polyolefin ratio of 95 / 5 to 50 / 50;

[0341] A mixture of solid and hollow glass reinforcing materials as defined above, in an amount of 50% to 70% by weight, particularly 50% to 65% by weight and more particularly 50% to 60% by weight; and

[0342] At least one prepolymer in an amount of 0% to 11% by weight, particularly 0.1% to 11%;

[0343] 0% to 5% of fillers and

[0344] Additives in an amount of 0% to 2% by weight, preferably 1% to 2% by weight,

[0345] The sum of the proportions of each component of the composition is equal to 100%.

[0346] In one embodiment, the composition does not contain polyamide 6 and 66.

[0347] All the features defined above for the above-defined use are valid for the composition itself.

[0348] Regarding fillers

[0349] The composition may further contain fillers. Envisaged fillers include conventional mineral fillers such as kaolin, magnesium oxide, slag, carbon black, expanded or unexpanded graphite, wollastonite, pigments such as titanium oxide and zinc sulfide, and antistatic fillers.

[0350] Advantageously, the composition, particularly suitable for injection molding, consists of:

[0351] An alloy consisting of at least one polyamide and at least one polyolefin as defined above, in an amount of 30% to 70% by weight, particularly 35% to 60% by weight and more particularly 40% to 50% by weight, with a polyamide / polyolefin ratio of 95 / 5 to 50 / 50;

[0352] A mixture of solid and hollow glass reinforcing materials as defined above, in an amount of 30% to 70% by weight, particularly 40% to 65% by weight and more particularly 50% to 60% by weight; and

[0353] At least one prepolymer in an amount of 0% to 11% by weight, particularly 0.1% to 11% by weight;

[0354] 0% to 5% of fillers, and

[0355] 0% to 2% by weight, preferably 1% to 2% by weight, of additives,

[0356] The sum of the proportions of each component of the composition is equal to 100%.

[0357] According to another aspect, the present invention relates to the use of a composition as defined above, said use for manufacturing articles, in particular for electronic products, for telecommunication applications or for data exchange, such as articles for autonomous vehicles or for applications connected to each other.

[0358] Advantageously, the article is manufactured by injection molding.

[0359] In other words, the present invention relates to a method for preparing an article, said article being in particular for electronic products, for telecommunication applications or for data exchange, such as for autonomous vehicles or for interconnected application uses, said method comprising in particular the step of injection molding a composition as defined above.

[0360] According to another aspect, the present invention relates to an article obtained by injection molding with a composition as defined above. Examples

[0361] The present invention will now be illustrated in more detail by the following examples, but is not limited thereto in any way.

[0362] The various polyamides and copolyamides of the present invention are prepared according to conventional techniques for the synthesis of polyamides and copolyamides.

[0363] Synthesis of CoPa 11 / 10T, representing various copolyamides:

[0364] The monomers aminoundecanoic acid, decanediamine and terephthalic acid are loaded together in a reactor according to the desired mass ratio. First, the medium is inerted to remove oxygen that can cause yellowing or secondary reactions. Water can also be loaded to improve heat exchange. Two temperature rises and pressure plateaus are carried out. The temperature (T°) and pressure conditions are selected to allow the medium to melt. After reaching the holding conditions, degassing is carried out to allow the polycondensation reaction. The medium gradually becomes viscous and the water of reaction formed is entrained by purging with nitrogen or applying a vacuum. When the stop condition related to the desired viscosity is reached, stirring is stopped and extrusion and granulation can be started.

[0365] The compositions (weight %) in Table 1 are prepared according to the following general scheme:

[0366] Compounding of the granules for preparing the formulation:

[0367] A twin-screw extruder, such as a Coperion ZSK 26 MC, having at least 1 lateral raw material inlet

[0368] Machine temperature: 270 °C

[0369] Screw speed: 250 rpm

[0370] Extruder output: 16 kg / h

[0371] Conversion

[0372] Wafers of 100 x 100 x 2 mm3 were manufactured by injection molding for measuring dielectric properties. The following parameters were used:

[0373] - ENGEL VICTORY 500, 160T hydraulic press

[0374] - Injection temperature (feed / nozzle): 265 °C / 280 °C

[0375] - Mold temperature: 100 °C

[0376] - Holding time: 10 s

[0377] - Material holding pressure: 700 bar

[0378] - Cooling time: 35 s

[0379] Dumbbell-shaped specimens according to ISO 527-2 1A were prepared by injection molding for measuring tensile mechanical properties. The following parameters were used:

[0380] - ENGEL VICTORY 500, 160T hydraulic press

[0381] - Injection temperature (feed / nozzle): 285 °C / 295 °C

[0382] - Mold temperature: 100 °C

[0383] - Holding time: 10 s

[0384] - Material holding pressure: 700 bar

[0385] - Cooling time: 15 s

[0386] The results obtained from the compositions of the present invention are shown in Tables 1 and 2 below:

[0387] Table 1

[0388]

[0389]

[0390] The comparative compositions are shown in Table 3 below:

[0391] Table 3

[0392]

[0393] I1 to I9: Inventions 1 to 9

[0394] C1 to C13: Comparative Compositions C1 to C13

[0395] N / A: Not Tested

[0396] PA11: Rilsan (Arkema)

[0397] PA11 / 10T (28 / 72 by weight)

[0398] PA11 / B10 (10 / 90 by weight)

[0399] Polypropylene PPH 5060: Non-grafted polypropylene homopolymer from Total

[0400] Orevac CA 100: Maleic anhydride grafted polypropylene (Arkema)

[0401] PA oligomer: PA11 mono-NH2

[0402] The antioxidant refers to an antioxidant of the phenolic type.

[0403] The secondary antioxidant corresponds to an antioxidant of the phosphite type.

[0404] NE glass fiber: NE solid glass fiber with a flat cross-section from Nitto Boseki

[0405] E glass fiber: E solid glass fiber with a circular cross-section from Nitto Boseki or Nippon Electric Glass

[0406] HM glass fiber: Solid fiber with a circular cross-section from AGY (High Modulus Glass Fiber)

[0407] Glass beads: Hollow (Hollowlite) glass beads

[0408] Dk, tanδ are measured according to ASTM D-2520-13

[0409] The tensile modulus (or elastic modulus E) is measured according to ISO 527-1 and 2:2012.

Claims

1. Use of a mixture of solid and hollow glass reinforcing materials and an alloy composed of at least one polyamide and at least one polyolefin, wherein the mixture of solid and hollow glass reinforcing materials contains 5% to 50% by weight, particularly 5% to 35% by weight, of hollow glass beads based on the total of the solid and hollow glass reinforcing materials, excluding polyamide 6 and 66, for the dry preparation, at 23 °C, of a composition having a modulus of at least 8 GPa, particularly at least 10 GPa, particularly at least 11 GPa, and a dielectric constant Dk less than or equal to 3.5, particularly less than or equal to 3.3, particularly less than or equal to 3.2, measured at 23 °C and 50% RH at a frequency of at least 1 GHz, particularly at least 2 GHz, particularly at least 3 GHz, in accordance with ASTM D - 2520 - 13.

2. Use according to claim 1, wherein the dielectric loss (tanδ) of the composition is less than or equal to 0.01, measured on a dry sample at 23 °C and 50% RH at a frequency of at least 1 GHz, particularly up to 2.4 GHz, in accordance with ASTM D - 2520 - 13.

3. Use according to claim 1 or 2, wherein the mixture of solid and hollow glass reinforcing materials, in addition to hollow glass beads, further comprises solid glass fibers selected from glass fibers with a circular cross - section, glass fibers with a flat cross - section, and mixtures thereof.

4. Use according to claim 3, wherein the mixture of glass reinforcing materials consists of 50% to 95% by weight of solid glass fibers and 5% to 50% by weight of hollow glass beads, particularly 65% to 95% by weight of solid glass fibers and 5% to 35% by weight of hollow glass beads.

5. Use according to any one of claims 1 to 4, wherein the alloy is composed of at least one polyamide and at least one polyolefin, and the weight ratio of polyamide / polyolefin is between 95 / 5 and 50 / 50.

6. Use according to any one of claims 1 to 5, wherein the at least one polyolefin is selected from grafted polyolefins, non - grafted polyolefins, and mixtures thereof, particularly mixtures thereof.

7. Use according to claim 6, wherein the reactive unit of the grafted polyolefin is selected from: esters of unsaturated carboxylic acids, such as alkyl acrylates or alkyl methacrylates, preferably the alkyl group has 1 to 24 carbon atoms, and examples of alkyl acrylates or alkyl methacrylates are in particular methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate; vinyl esters of saturated carboxylic acids, such as vinyl acetate or vinyl propionate.

8. Use according to claim 6 or 7, wherein the grafted polyolefin is based on propylene.

9. Use according to claim 6, wherein the non-grafted polyolefin is selected from ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene, 1-tetracosene, 1-hexacosene, 1-octacosene and 1-triacontene, preferably propylene or ethylene or dienes such as butadiene, isoprene or 1,4-hexadiene.

10. Use according to any one of claims 6 and 9, wherein the non-grafted polyolefin is based on propylene.

11. Use according to any one of claims 5 to 10, wherein the alloy consists of at least one polyamide and a mixture of a grafted polyolefin based on polypropylene and a non-grafted polyolefin based on polypropylene.

12. Use according to any one of claims 1 to 11, wherein the at least one polyamide is selected from semi-crystalline polyamides, amorphous polyamides and mixtures thereof.

13. Use according to any one of claims 1 to 12, wherein the alloy consists of a single polyamide which is an amorphous polyamide and at least one polyolefin.

14. Use according to claim 13, wherein the amorphous polyamide is a polyamide of formula A / XY, wherein: A is an aliphatic repeating unit obtained by polycondensation as follows: At least one C6 to C 18 , preferably C6 to C 12 , more preferably C 10 to C 12 amino acid, or At least one C6 to C 18 , preferably C6 to C 12 , more preferably C 10 to C 12 lactam, or At least one C4-C 36 , preferably C6-C 18 , preferably C6-C 12 , more preferably C 10 -C 12 aliphatic diamine Ca, and at least one C4-C 36 , preferably C6-C 18 , preferably C6-C 12 , more preferably C8-C 12 dicarboxylic acid Cb; XY is an aliphatic repeating unit obtained by polycondensation as follows: at least one alicyclic diamine, or at least one straight-chain or branched aliphatic diamine X and at least one aromatic dicarboxylic acid or at least one aliphatic dicarboxylic acid Y.

15. Use according to claim 13 or 14, wherein the amorphous polyamide is selected from 11 / B10, 12 / B10, 11 / BI / BT, 11 / BI, in particular 11 / B10.

16. Use according to any one of claims 1 to 12, wherein the alloy consists of a single semi-crystalline polyamide or a mixture of two semi-crystalline polyamides and at least one polyolefin.

17. Use according to claim 16, wherein the semi-crystalline polyamide is selected from aliphatic polyamides, in particular long-chain polyamides, aryl-aliphatic polyamides and semi-aromatic polyamides.

18. Use according to claim 16 or 17, wherein the polyamide mixture is a mixture of an aliphatic polyamide, in particular a long-chain polyamide, and an aryl-aliphatic polyamide.

19. Use according to claim 17 or 18, wherein the aliphatic polyamide is selected from PA610, PA612, PA1010, PA1012, PA1212, PA11 and PA 12, in particular PA1010, PA1012, PA1212, PA11, PA 12.

20. Use according to claim 17 or 18, wherein the aryl-aliphatic polyamide is selected from MXD6, MXD10, MXD12.

21. Use according to claim 17, wherein the semi-aromatic polyamide is selected from PA11 / 9T, PA11 / 10T, PA 11 / 12T, PA12 / 9T, PA12 / 10T, PA12 / 12T.

22. Use according to any one of claims 11 to 15, wherein the alloy consists of a single polyamide as an amorphous polyamide and a mixture of a graft polyolefin based on polypropylene and a non-grafted polyolefin based on polypropylene.

23. Use according to claims 11 and any one of claims 16 to 21, wherein the alloy consists of a mixture of two semi-crystalline polyamides and a mixture of a graft polyolefin based on polypropylene and a non-grafted polyolefin based on polypropylene.

24. Use according to one of claims 1 to 23, wherein the composition contains additives.

25. Use according to one of claims 1 to 24, wherein the composition contains at least one prepolymer, in particular a monofunctional NH2, in particular based on PA11.

26. A composition, in particular for injection molding, the composition comprising: An alloy composed of at least one polyamide and at least one polyolefin as defined in one of claims 1 to 23, in an amount of 30% to 70% by weight, particularly 35% to 60% by weight, and more particularly 40% to 50% by weight, with a polyamide / polyolefin ratio of 95 / 5 to 50 / 50; A mixture of solid and hollow glass reinforcing materials as defined in one of claims 1 to 23, in an amount of 30% to 70% by weight, particularly 40% to 65% by weight, and more particularly 50% to 60% by weight; Excluding polyamide 6 and 66, and At least one prepolymer in an amount of 0% to 11% by weight, particularly 0.1% to 11%; Fillers in an amount of 0% to 5% by weight, and Additives in an amount of 0% to 2% by weight, preferably 1% to 2% by weight, The sum of the proportions of each component of the composition equals 100%.

27. Use of a composition as defined in one of claims 1 to 25 for manufacturing an article, particularly for electronic products, for telecommunication applications or for data exchange, such as an article for autonomous vehicles or for interconnect applications.

28. The use according to claim 27, characterized in that The article is manufactured by injection molding.

29. An article obtained by injection molding with a composition as defined in one of claims 1 to 25.

Images