Polyamide compositions having high modulus and low dielectric constant, and uses thereof

Abstract

The present invention relates to the use of a mixture of solid and hollow glass reinforcements with an alloy consisting of at least one polyamide and at least one polyolefin, the mixture of solid and hollow glass reinforcements comprising 5 to 50% by weight of hollow glass beads relative to the total weight of the solid and hollow glass reinforcements, in particular 5 to 35% by weight of hollow glass beads relative to the total weight of the solid and hollow glass reinforcements, for the preparation of a composition having a modulus of elasticity in the dry state at 23°C of at least 8 GPa, in particular at least 10 GPa, in particular at least 11 GPa, and a dielectric constant Dk of 3.5 or less, in particular 3.3 or less, in particular 3.2 or less, measured according to ASTM D-2520-13 at a frequency of at least 1 GHz, in particular at a frequency of at least 2 GHz, in particular at least 3 GHz, at 23°C and 50% RH.

Description

[Technical Field]

[0001] The present invention relates to the use of a mixture of solid and hollow glass strengthening agents with an alloy comprising at least one polyamide and at least one polyolefin for producing a composition having a high modulus of elasticity and a low dielectric constant, as well as a method for producing the same and the composition. [Background technology]

[0002] Original equipment manufacturers (OEMs), particularly those in electronics, telecommunications, or data exchange applications, such as for autonomous vehicles and interconnection, are showing increasing interest in materials used for protection or cladding of such low dielectric constant devices.

[0003] Indeed, the advantage of integrating such materials into, for example, the casing of a mobile phone, is to ensure signal integrity in antenna applications and to guarantee perfect high-speed signal transmission.

[0004] Furthermore, in the context of data exchange, the dielectric constant must be as low as possible to ensure the fastest possible data exchange.

[0005] Therefore, the main challenge for such applications is to have the lowest dielectric properties while maintaining a very hard protective or cladding material. However, in order to obtain a hard protective or cladding material, it is often necessary to use glass fibers that give the material a high modulus of elasticity, and therefore a higher rigidity.

[0006] Nevertheless, it is known that, for example, the presence of standard glass fibers in a telephone shell ensures good rigidity of the shell, but the dielectric constant increases significantly, thus interfering with signal transmission.

[0007] Therefore, it is necessary to have a material that exhibits both rigidity and, consequently, high elasticity, while maintaining a low dielectric constant to ensure fully high-speed signal transmission or the fastest possible data exchange.

Summary of the Invention

[0008] Therefore, the above-described problems are solved by the present invention. The present invention relates to the use of a mixture of solid and hollow glass reinforcing agents with an alloy consisting of at least one polyamide and at least one polyolefin. The mixture of solid and hollow glass reinforcing agents contains 5 to 50% by weight of hollow glass beads, particularly 5 to 35% by weight of hollow glass beads, based on the total of solid and hollow glass reinforcing agents, and is used for the preparation of a composition. The composition has a modulus of elasticity equal to at least 8 GPa, particularly equal to at least 10 GPa, particularly equal to at least 11 GPa, in a dry state at 23°C, and a dielectric constant Dk of 3.5 or less, particularly 3.3 or less, particularly 3.2 or less, measured at a frequency of at least 1 GHz, particularly at least 2 GHz, particularly at least 3 GHz, 23°C, 50% RH, in accordance with ASTM D-2520-13.

[0009] In other words, the present invention relates to the use of a mixture of solid and hollow glass reinforcing agents with an alloy consisting of at least one polyamide and at least one polyolefin. The mixture of solid and hollow glass reinforcing agents contains 5 to 50% by weight of hollow glass beads, particularly 5 to 35% by weight of hollow glass beads, based on the total of solid and hollow glass reinforcing agents, and is used to at least preserve the modulus of elasticity and reduce the dielectric constant of a composition relative to a composition containing the alloy and glass reinforcing agent without the solid glass reinforcing agent, or the alloy and glass reinforcing agent without the hollow glass reinforcing agent. The modulus of elasticity of the composition in a dry state at 23°C is equal to at least 8 GPa, particularly equal to at least 10 GPa, particularly equal to at least 11 GPa, and the dielectric constant of the composition is measured at a frequency of at least 1 GHz, particularly at least 2 GHz, particularly at least 3 GHz, 23°C, 50% RH, in accordance with ASTM D-2520-13, and is 3.5 or less, particularly 3.3 or less, particularly 3.2 or less.

[0010] In one embodiment, the composition of the present invention does not contain polyamide 6 and 66.

[0011] Thus, the inventors unexpectedly combined solid and hollow glass reinforcing agents with an alloy composed of at least one polyamide and at least one polyolefin, and further, when the hollow glass beads are in a specific ratio with respect to the total of the solid and hollow glass reinforcing agents, a composition having a high elastic modulus of at least 8 GPa, particularly at least 10 GPa, particularly at least 11 GPa, and a low dielectric constant Dk of 3.5 or less, particularly 3.3 or less, particularly 3.2 or less can be prepared. Therefore, it has been found that it is possible to have a rigid material that can ensure complete high-speed signal transmission or can have data exchange as fast as possible.

[0012] Differences in elastic moduli (e.g., tensile elastic modulus, flexural elastic modulus, etc.) are distinguished. The inventors have found that when considering the flexural elastic modulus, it is always lower than the tensile elastic modulus.

[0013] These elastic moduli can be affected by temperature and the moisture level in the sample.

[0014] In one embodiment, the elastic modulus defined above corresponds to both the flexural elastic modulus and the tensile elastic modulus. The flexural elastic modulus is measured according to ISO 178:2010, and the tensile elastic modulus (or elastic coefficient E) is measured according to ISO 527-1 and 2:2012.

[0015] In other embodiments, the elastic modulus defined above corresponds to the flexural elastic modulus and is measured as described above.

[0016] In other embodiments, the elastic modulus defined above corresponds to the tensile elastic modulus and is measured as described above.

[0017] The dielectric constant is defined as the ratio of the dielectric constant ε of the material to the permittivity of free space. This is represented by k or Dk and is measured in accordance with ASTM D-2520-13. This is the relative dielectric constant.

[0018] This is measured at 23°C and 50% relative humidity (RH) using pre-dried samples, particularly those dried at 80°C for 5 days.

[0019] In one embodiment, the composition has a dry modulus of at least 8 GPa at 23°C and a dielectric constant Dk of 3.5 or less at a frequency of at least 1 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus and the flexural modulus.

[0020] In one embodiment, the composition has a dry modulus of at least 10 GPa at 23°C and a dielectric constant Dk of 3.5 or less at a frequency of at least 1 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus and the flexural modulus.

[0021] In one embodiment, the composition has a dry modulus of at least 11 GPa at 23°C and a dielectric constant Dk of 3.5 or less at a frequency of at least 1 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus and the flexural modulus.

[0022] In one embodiment, the composition has a dry modulus of at least 8 GPa at 23°C and a dielectric constant Dk of 3.3 or less at a frequency of at least 1 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus and the flexural modulus.

[0023] In one embodiment, the composition has a dry modulus of at least 10 GPa at 23°C and a dielectric constant Dk of 3.3 or less at a frequency of at least 1 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus and the flexural modulus.

[0024] In one embodiment, the composition has a dry modulus of at least 11 GPa at 23°C and a dielectric constant Dk of 3.3 or less at a frequency of at least 1 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus and the flexural modulus.

[0025] In one embodiment, the composition has a dry modulus of at least 8 GPa at 23°C and a dielectric constant Dk of 3.2 or less at a frequency of at least 1 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus and the flexural modulus.

[0026] In one embodiment, the composition has a dry modulus of at least 10 GPa at 23°C and a dielectric constant Dk of 3.2 or less at a frequency of at least 1 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus and the flexural modulus.

[0027] In one embodiment, the composition has a dry modulus of at least 11 GPa at 23°C and a dielectric constant Dk of 3.2 or less at a frequency of at least 1 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus and the flexural modulus.

[0028] In one embodiment, the composition has a dry modulus of at least 8 GPa at 23°C and a dielectric constant Dk of 3.5 or less at frequencies up to 2.4 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus and the flexural modulus.

[0029] In one embodiment, the composition has a dry modulus of at least 10 GPa at 23°C and a dielectric constant Dk of 3.5 or less at frequencies up to 2.4 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus and the flexural modulus.

[0030] In one embodiment, the composition has a dry modulus of at least 11 GPa at 23°C and a dielectric constant Dk of 3.5 or less at frequencies up to 2.4 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus and the flexural modulus.

[0031] In one embodiment, the composition has a dry modulus of at least 8 GPa at 23°C and a dielectric constant Dk of 3.3 or less at frequencies up to 2.4 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus and the flexural modulus.

[0032] In one embodiment, the composition has a dry modulus of at least 10 GPa at 23°C and a dielectric constant Dk of 3.3 or less at frequencies up to 2.4 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus and the flexural modulus.

[0033] In one embodiment, the composition has a dry modulus of at least 11 GPa at 23°C and a dielectric constant Dk of 3.3 or less at frequencies up to 2.4 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus and the flexural modulus.

[0034] In one embodiment, the composition has a dry modulus of at least 8 GPa at 23°C and a dielectric constant Dk of 3.2 or less at frequencies up to 2.4 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus and the flexural modulus.

[0035] In one embodiment, the composition has a dry modulus of at least 10 GPa at 23°C and a dielectric constant Dk of 3.2 or less at frequencies up to 2.4 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus and the flexural modulus.

[0036] In one embodiment, the composition has a dry modulus of at least 11 GPa at 23°C and a dielectric constant Dk of 3.2 or less at frequencies up to 2.4 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus and the flexural modulus.

[0037] In one embodiment, the composition has a dry modulus of at least 8 GPa at 23°C and a dielectric constant Dk of 3.5 or less at a frequency of at least 1 GHz and 50% RH, where the modulus corresponds to the flexural modulus.

[0038] In one embodiment, the composition has a dry modulus of at least 10 GPa at 23°C and a dielectric constant Dk of 3.5 or less at a frequency of at least 1 GHz and 50% RH, where the modulus corresponds to the flexural modulus.

[0039] In one embodiment, the composition has a dry modulus of at least 11 GPa at 23°C and a dielectric constant Dk of 3.5 or less at a frequency of at least 1 GHz and 50% RH, where the modulus corresponds to the flexural modulus.

[0040] In one embodiment, the composition has a dry modulus of at least 8 GPa at 23°C and a dielectric constant Dk of 3.3 or less at a frequency of at least 1 GHz and 50% RH, where the modulus corresponds to the flexural modulus.

[0041] In one embodiment, the composition has a dry modulus of at least 10 GPa at 23°C and a dielectric constant Dk of 3.3 or less at a frequency of at least 1 GHz and 50% RH, wherein the modulus corresponds to the flexural modulus.

[0042] In one embodiment, the composition has a dry modulus of at least 11 GPa at 23°C and a dielectric constant Dk of 3.3 or less at a frequency of at least 1 GHz and 50% RH, where the modulus corresponds to the flexural modulus.

[0043] In one embodiment, the composition has a dry modulus of at least 8 GPa at 23°C and a dielectric constant Dk of 3.2 or less at a frequency of at least 1 GHz and 50% RH, where the modulus corresponds to the flexural modulus.

[0044] In one embodiment, the composition has a dry modulus of at least 10 GPa at 23°C and a dielectric constant Dk of 3.2 or less at a frequency of at least 1 GHz and 50% RH, where the modulus corresponds to the flexural modulus.

[0045] In one embodiment, the composition has a dry modulus of at least 11 GPa at 23°C and a dielectric constant Dk of 3.2 or less at a frequency of at least 1 GHz and 50% RH, where the modulus corresponds to the flexural modulus.

[0046] In one embodiment, the composition has a dry modulus of at least 8 GPa at 23°C and a dielectric constant Dk of 3.5 or less at frequencies up to 2.4 GHz and 50% RH, where the modulus corresponds to the flexural modulus.

[0047] In one embodiment, the composition has a dry modulus of at least 10 GPa at 23°C and a dielectric constant Dk of 3.5 or less at frequencies up to 2.4 GHz and 50% RH, where the modulus corresponds to the flexural modulus.

[0048] In one embodiment, the composition has a dry modulus of at least 11 GPa at 23°C and a dielectric constant Dk of 3.5 or less at frequencies up to 2.4 GHz and 50% RH, where the modulus corresponds to the flexural modulus.

[0049] In one embodiment, the composition has a dry modulus of at least 8 GPa at 23°C and a dielectric constant Dk of 3.3 or less at frequencies up to 2.4 GHz and 50% RH, where the modulus corresponds to the flexural modulus.

[0050] In one embodiment, the composition has a dry modulus of at least 10 GPa at 23°C and a dielectric constant Dk of 3.3 or less at frequencies up to 2.4 GHz and 50% RH, where the modulus corresponds to the flexural modulus.

[0051] In one embodiment, the composition has a dry modulus of at least 11 GPa at 23°C and a dielectric constant Dk of 3.3 or less at frequencies up to 2.4 GHz and 50% RH, where the modulus corresponds to the flexural modulus.

[0052] In one embodiment, the composition has a dry modulus of at least 8 GPa at 23°C and a dielectric constant Dk of 3.2 or less at frequencies up to 2.4 GHz and 50% RH, where the modulus corresponds to the flexural modulus.

[0053] In one embodiment, the composition has a dry modulus of at least 10 GPa at 23°C and a dielectric constant Dk of 3.2 or less at frequencies up to 2.4 GHz and 50% RH, where the modulus corresponds to the flexural modulus.

[0054] In one embodiment, the composition has a dry modulus of at least 11 GPa at 23°C and a dielectric constant Dk of 3.2 or less at frequencies up to 2.4 GHz and 50% RH, where the modulus corresponds to the flexural modulus.

[0055] In one embodiment, the composition has a dry modulus of at least 8 GPa at 23°C and a dielectric constant Dk of 3.5 or less at a frequency of at least 1 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus.

[0056] In one embodiment, the composition has a dry modulus of at least 10 GPa at 23°C and a dielectric constant Dk of 3.5 or less at a frequency of at least 1 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus.

[0057] In one embodiment, the composition has a dry modulus of at least 11 GPa at 23°C and a dielectric constant Dk of 3.5 or less at a frequency of at least 1 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus.

[0058] In one embodiment, the composition has a dry modulus of at least 8 GPa at 23°C and a dielectric constant Dk of 3.3 or less at a frequency of at least 1 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus.

[0059] In one embodiment, the composition has a dry modulus of at least 10 GPa at 23°C and a dielectric constant Dk of 3.3 or less at a frequency of at least 1 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus.

[0060] In one embodiment, the composition has a dry modulus of at least 11 GPa at 23°C and a dielectric constant Dk of 3.3 or less at a frequency of at least 1 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus.

[0061] In one embodiment, the composition has a dry modulus of at least 8 GPa at 23°C and a dielectric constant Dk of 3.2 or less at a frequency of at least 1 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus.

[0062] In one embodiment, the composition has a dry modulus of at least 10 GPa at 23°C and a dielectric constant Dk of 3.2 or less at a frequency of at least 1 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus.

[0063] In one embodiment, the composition has a dry modulus of at least 11 GPa at 23°C and a dielectric constant Dk of 3.2 or less at a frequency of at least 1 GHz and 50% RH, wherein the modulus corresponds to the tensile modulus.

[0064] In one embodiment, the composition has a dry modulus of at least 8 GPa at 23°C and a dielectric constant Dk of 3.5 or less at frequencies up to 2.4 GHz and 50% RH, where the modulus corresponds to the tensile modulus.

[0065] In one embodiment, the composition has a dry modulus of at least 10 GPa at 23°C and a dielectric constant Dk of 3.5 or less at frequencies up to 2.4 GHz and 50% RH, where the modulus corresponds to the tensile modulus.

[0066] In one embodiment, the composition has a dry modulus of at least 11 GPa at 23°C and a dielectric constant Dk of 3.5 or less at frequencies up to 2.4 GHz and 50% RH, where the modulus corresponds to the tensile modulus.

[0067] In one embodiment, the composition has a dry modulus of at least 8 GPa at 23°C and a dielectric constant Dk of 3.3 or less at frequencies up to 2.4 GHz and 50% RH, where the modulus corresponds to the tensile modulus.

[0068] In one embodiment, the composition has a dry modulus of at least 10 GPa at 23°C and a dielectric constant Dk of 3.3 or less at frequencies up to 2.4 GHz and 50% RH, where the modulus corresponds to the tensile modulus.

[0069] In one embodiment, the composition has a dry modulus of at least 11 GPa at 23°C and a dielectric constant Dk of 3.3 or less at frequencies up to 2.4 GHz and 50% RH, where the modulus corresponds to the tensile modulus.

[0070] In one embodiment, the composition has a dry modulus of at least 8 GPa at 23°C and a dielectric constant Dk of 3.2 or less at frequencies up to 2.4 GHz and 50% RH, where the modulus corresponds to the tensile modulus.

[0071] In one embodiment, the composition has a dry modulus of at least 10 GPa at 23°C and a dielectric constant Dk of 3.2 or less at frequencies up to 2.4 GHz and 50% RH, where the modulus corresponds to the tensile modulus.

[0072] In one embodiment, the composition has a dry modulus of at least 11 GPa at 23°C and a dielectric constant Dk of 3.2 or less at frequencies up to 2.4 GHz and 50% RH, where the modulus corresponds to the tensile modulus.

[0073] The measurement of dielectric loss (tan delta or tan(δ)) (or power factor (tan delta or tan(δ))) is used to determine the insulating properties of a composition.

[0074] Advantageously, the dielectric loss (tan delta) of the composition is less than or equal to 0.01, as measured in accordance with ASTM D-2520-13, at a frequency of at least 1 GHz, particularly up to 2.4 GHz, at 23°C, and 50% RH, using a dry sample.

[0075] The samples were then pre-dried, particularly at 80°C for 5 days, and tested at 23°C and 50% RH.

[0076] In one embodiment, the composition has a dry modulus and dielectric constant Dk at 23°C, as defined above in various embodiments, and a dielectric loss (tan delta) of 0.01 or less, as measured in a dry sample at the same frequency, 23°C, and 50%RH as the dielectric constant in the embodiments. [Modes for carrying out the invention]

[0077] Regarding solid and hollow glass strengthening agents Solid glass strengthening agent A solid glass strengthening agent is a glass fiber material having a solid (as opposed to hollow) structure, which can take on any shape as long as it is solid.

[0078] These shapes may have a circular or non-circular cross-section.

[0079] A shape with a circular cross-section is defined as a shape that has an equal distance from the center of the shape to any point on its periphery, and thus represents a perfect or nearly perfect circle.

[0080] Therefore, any glass shape that does not have a perfect or nearly perfect circle is defined as a shape with a flattened cross-section.

[0081] Examples of flattened cross-sectional shapes that are not limited to flattened shapes include elliptical, oblong, or cocoon-shaped, star-shaped, flake-shaped, cruciform, polygonal, and ring-shaped shapes.

[0082] The solid glass shape may be short solid glass fibers, preferably 2 to 13 mm in length, and more preferably 3 to 8 mm, before using the composition.

[0083] Solid glass fibers may be as follows: -Having a circular cross-section with a diameter of 4 μm to 25 μm, preferably 4 μm to 15 μm, - Or it has a non-circular cross-section with an L / D ratio (where L represents the maximum cross-sectional dimension of the fiber and D represents the minimum cross-sectional dimension of the fiber) of 2 to 8, particularly 2 to 4. L and D can be measured by scanning electron microscopy (SEM).

[0084] Hollow glass strengthening agent Hollow glass strengthening agents are glass fiber materials with a hollow (as opposed to solid) structure, and as long as they are hollow, they can have any shape, just like solid glass strengthening agents.

[0085] The hollow glass shape may be short hollow glass fibers, preferably having a length of 2 to 13 mm, and more preferably 3 to 8 mm, before using the composition.

[0086] Hollow glass fiber refers to glass fiber in which the hollow (or pore or window) within the fiber is not necessarily concentric with the outer diameter of the fiber.

[0087] Hollow glass fibers can be as follows: - It has a circular cross-section with a diameter of 7.5 μm to 75 μm, preferably 9 μm to 25 μm, and more preferably 10 μm to 12 μm.

[0088] It is clear that the diameter of the hollow (the term "hollow" can also be called a hole or window) is not equal to the outer diameter of the hollow glass fiber.

[0089] Advantageously, the diameter of the hollow (or hole or window) is 10% to 80%, particularly 60% to 80%, of the outer diameter of the hollow fiber. - Or it has a non-circular cross-section with an L / D ratio (where L represents the maximum cross-sectional dimension of the fiber and D represents the minimum cross-sectional dimension of the fiber) of 2 to 8, particularly 2 to 4. L and D can be measured by scanning electron microscopy (SEM).

[0090] The mixture of solid and hollow glass strengthening agents contains 5 to 50% by weight of hollow glass beads, and in particular 5 to 35% by weight of hollow glass beads, relative to the total amount of solid and hollow glass strengthening agents.

[0091] In one embodiment, the mixture of solid and hollow glass strengthening agents contains 10 to 50% by weight of hollow glass beads, and in particular 10 to 35% by weight of hollow glass beads, relative to the total of the solid and hollow glass strengthening agents.

[0092] In one embodiment, the mixture of solid and hollow glass reinforcing agents includes, in addition to hollow glass beads, solid glass fibers selected from circular cross-section glass fibers, flattened cross-section glass fibers, and mixtures thereof.

[0093] In one embodiment, the mixture of solid and hollow glass strengthening agents contains 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 strengthening agents, wherein the hollow glass beads represent the total proportion of the hollow strengthening agents.

[0094] In this last embodiment, the mixture of solid and hollow glass reinforcing agents includes, in addition to the hollow glass beads that constitute the whole of the hollow reinforcing agent, solid glass fibers selected from circular cross-section glass fibers, flattened cross-section glass fibers, and mixtures thereof.

[0095] Advantageously, the glass strengthening agent mixture consists of 50-95% by weight of solid glass fibers and 5-50% by weight of hollow glass beads, particularly 65-95% by weight of solid glass fibers and 5-35% by weight of hollow glass beads.

[0096] Advantageously, the glass strengthening agent mixture consists of 50-90% by weight of solid glass fibers and 10-50% by weight of hollow glass beads, particularly 65-90% by weight of solid glass fibers and 10-35% by weight of hollow glass beads.

[0097] Advantageously, the solid glass fiber is a glass fiber having a non-circular cross-section.

[0098] In one embodiment, the solid glass strengthening agent is a glass fiber having a Dk > 5 at frequencies from 1 MHz to 5 GHz, and particularly a Dk > 5 and a Df < 0.005 at a frequency of 1 GHz.

[0099] Advantageously, the solid glass reinforcing agent is a glass fiber having a non-circular cross-section and an elastic modulus of less than 76 GPa as measured in accordance with ASTM C 1557-03.

[0100] For an alloy consisting of at least one polyamide and at least one polyolefin

[0101] Advantageously, the alloy comprises at least one polyamide and at least one polyolefin, with a polyamide / polyolefin weight ratio of 95 / 5 to 50 / 50.

[0102] Polyolefins: The polyolefin in the composition may be a grafted (or functionalized), non-grafted (or non-functionalized) polyolefin, or a mixture thereof.

[0103] Grafted polyolefins can be polymers of alpha-olefins having reactive units (functionality), such reactive units being acids, anhydrides, or epoxy functional groups. Examples include the aforementioned non-grafted polyolefins that are still grafted, copolymerized, or terpolymerized by unsaturated epoxides such as glycidyl (meth)acrylate, or by carboxylic acids or their corresponding salts, or by esters such as (meth)acrylic acid (which can be completely or partially neutralized by metals such as Zn), or even by carboxylic acid anhydrides such as maleic anhydride.

[0104] Advantageously, the grafted polyolefin is selected from vinyl esters of unsaturated carboxylic acids, such as alkyl acrylates or alkyl methacrylates, preferably the alkyl having 1 to 24 carbon atoms, and examples of alkyl acrylates or alkyl methacrylates include, in particular, methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and 2-ethylhexyl acrylate; for example, vinyl esters of saturated carboxylic acids, such as vinyl acetate or vinyl propionate.

[0105] Advantageously, the grafted polyolefin defined above is polypropylene-based.

[0106] Non-grafted polyolefins are typically homopolymers or copolymers of alphaolefins or diolefins, 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 which can be mixed with a compatible and functional compatibilizer, or dienes such as butadiene, for example, maleate-Lotader® or maleate-polyethylene, isoprene, or polyethylene mixed with 1,4-hexadiene.

[0107] In particular, the alpha-olefin homopolymer is selected from low-density polyethylene (LDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), and metallocene polyethylene.

[0108] In particular, alpha-olefin or diolefin copolymers are selected from ethylene / alpha-olefin polymers such as ethylene-propylene, ethylene-butylene, ethylene-propylene-diene monomer, and ethylene-octene, and are used alone or in combination with polyethylene (PE).

[0109] Advantageously, the non-grafted polyolefin defined above is polypropylene-based.

[0110] The polyolefin in the composition may be crosslinked, uncrosslinked, or a mixture of at least one crosslinked and / or at least one uncrosslinked.

[0111] Cross-linked polyolefins 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 a polyamide.

[0112] The crosslinked polyolefin is derived from the reaction between two or more products having reactive groups.

[0113] Specifically, if the polyolefin is a crosslinked polyolefin, it is obtained from at least one product (A) containing an unsaturated epoxide and at least one product (B) containing an unsaturated carboxylic acid anhydride.

[0114] Product (A) is preferably a polymer containing an unsaturated epoxide, which is introduced into the polymer by either grafting or copolymerization.

[0115] Unsaturated epoxides can be selected from the following epoxides in particular: - Aliphatic glycidyl esters such as allyl glycidyl ether, vinyl glycidyl ether, glycidyl maleate and glycidyl itaconicate, glycidyl acrylate and glycidyl methacrylate, and aliphatic glycidyl ethers, Alicyclic glycidyl esters and alicyclic glycidyl ethers such as 2-cyclohexene-1-glycidyl ether, cyclohexene-4,5-diglycidylcarboxylate, cyclohexene-4-glycidylcarboxylate, 5-norbornene-2-methyl-2-glycidylcarboxylate, and endo-cis-bicyclo(2,2,1)-5-heptene-2,3-diglycidyldicarboxylate.

[0116] According to the first form, product (A) is a polyolefin grafted with an unsaturated epoxide. Polyolefin is understood to mean a homopolymer or copolymer containing one or more olefin units, such as ethylene, propylene, butene-1 units, or any other alpha-olefin units. Examples of polyolefins include: -Polyethylene including low-density polyethylene (LDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), and very low-density polyethylene (VLDPE); polypropylene; ethylene / propylene copolymers; elastomeric polyolefins such as ethylene-propylene (EPR or EPM) or ethylene-propylene-diene monomer (EPDM); or metallocene polyethylenes obtained by monosite catalysts; -Styrene / ethylene-butene / styrene (SEBS) block copolymers; styrene / butadiene / styrene (SBS) block copolymers; styrene / isoprene / styrene (SIS) block copolymers; or styrene / ethylene-propylene / styrene block copolymers; - A copolymer of ethylene with at least one product selected from salts of unsaturated carboxylic acids, esters of unsaturated carboxylic acids, and vinyl esters of saturated carboxylic acids. The polyolefin may be a copolymer of ethylene with alkyl (meth)acrylate, or a copolymer of ethylene with vinyl acetate.

[0117] According to the second embodiment, product (A) is a copolymer of alpha-olefin and unsaturated epoxide, preferably a copolymer of ethylene and unsaturated epoxide. The amount of unsaturated epoxide is preferably up to 15% by weight of copolymer (A), and the amount of ethylene is at least 50% by weight of copolymer (A).

[0118] More specifically, copolymers of ethylene, saturated vinyl carboxylate, and unsaturated epoxide, and copolymers of ethylene, alkyl (meth)acrylate, and unsaturated epoxide may be mentioned. The alkyl in (meth)acrylate has 2 to 10 carbon atoms. Examples of alkyl acrylates or methacrylates that can be used include methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and 2-ethylhexyl acrylate.

[0119] 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, a product sold by Arkema under the trade name LOTADER® AX8900 may be used.

[0120] According to another embodiment of the present invention, product (A) is a product having two epoxide functional groups, such as bisphenol A diglycidyl ether (DGEBA).

[0121] Product (B) is preferably a polymer containing an unsaturated carboxylic acid anhydride, which is introduced into the polymer by either grafting or copolymerization.

[0122] Examples of unsaturated dicarboxylic acid anhydrides that are useful as components of product (B) include maleic anhydride, itaconic anhydride, citraconic anhydride, and tetrahydrophthalic anhydride.

[0123] According to the first embodiment, product (B) is a polyolefin grafted with an unsaturated carboxylic acid anhydride. As described above, a polyolefin is a homopolymer or copolymer comprising one or more olefin units such as ethylene, propylene, or butene-1 units, or any other alpha-olefin units. This polyolefin can be selected from the examples of polyolefins listed above for product (A), in particular, when product (A) is a polyolefin grafted with an unsaturated epoxide.

[0124] According to the second embodiment, product (B) is a copolymer of an alpha-olefin and an unsaturated carboxylic acid anhydride, preferably a copolymer of ethylene and an unsaturated carboxylic acid anhydride. The amount of the unsaturated carboxylic acid anhydride is preferably up to 15% by weight of copolymer (B), and the amount of ethylene is at least 50% by weight of copolymer (B).

[0125] Specifically, copolymers of ethylene, saturated vinyl carboxylate, and unsaturated carboxylic acid anhydride, and copolymers of ethylene, alkyl (meth)acrylate, and unsaturated carboxylic acid anhydride may be mentioned. The alkyl in (meth)acrylate preferably has 2 to 10 carbon atoms. The alkyl acrylate or methacrylate can be selected from the above for product (A).

[0126] According to an advantageous version of the present invention, product (B) is a copolymer of ethylene, an alkyl (meth)acrylate, and an unsaturated carboxylic acid anhydride. Preferably, product (B) is a copolymer of ethylene, an ethyl acrylate, and maleic anhydride, or a copolymer of ethylene, butyl acrylate, and maleic anhydride. In particular, products sold by ARKEMA under trade names LOTADER® 4700 and LOTADER® 3410 may be used.

[0127] Even if a portion of the maleic anhydride in product (B) according to the first and second forms described above is partially hydrolyzed, this is not outside the scope of the present invention.

[0128] The weights of product (A) and product (B) (encoded as [A] and [B] respectively) are such that the ratio of [B] / [A] is between 3 and 14, preferably between 4 and 9.

[0129] In the composition according to the present invention, the crosslinked polyolefin may also be obtained from the above products (A) and (B), and at least one product (C), the product (C) comprising an unsaturated carboxylic acid or an alpha-omega-aminocarboxylic acid.

[0130] Product (C) is preferably a polymer comprising an unsaturated carboxylic acid or an alpha-omega-aminocarboxylic acid, one of which is introduced into the polymer by copolymerization.

[0131] Examples of unsaturated carboxylic acids that can be used as components of product (C) include acrylic acid, methacrylic acid, and the carboxylic acid anhydrides mentioned above as components of product (B), which are completely hydrolyzed.

[0132] Examples of alpha-omega-aminocarboxylic acids suitable for use as components of product (C) include 6-aminohexanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.

[0133] Product (C) may be a copolymer of an alpha-olefin and an unsaturated carboxylic acid, and more preferably, a copolymer of ethylene and an unsaturated carboxylic acid. In particular, completely hydrolyzed copolymers of product (B) are mentioned.

[0134] According to an advantageous version of the present invention, product (C) is a copolymer of ethylene and (meth)acrylic acid, or a copolymer of ethylene, alkyl (meth)acrylate, and (meth)acrylic acid. The amount of (meth)acrylic acid may be up to 10% by weight of copolymer (C), preferably 0.5 to 5% by weight. The amount of alkyl (meth)acrylate is generally 5 to 40% by weight of copolymer (C).

[0135] Advantageously, product (C) is a copolymer of ethylene, butyl acrylate, and acrylic acid, such as Exxon Mobil's Escor® 5000.

[0136] Preferably, product (C) is a copolymer of ethylene, butyl acrylate, and acrylic acid. In particular, the product sold by BASF under the trade name LUCALENER® 3110 may be used.

[0137] The crosslinked polyolefin dispersed phase can, of course, be produced by reacting one or more products (A) with one or more products (B), and optionally one or more products (C).

[0138] As already described in International Publication No. 2011 / 015790, a catalyst can be used to accelerate the reaction of the reactive functional groups of products (A) and (B). Examples of catalysts are described in this document and can be used in amounts of 0.1 to 3% by weight, preferably 0.5 to 1% by weight, of the total weight of products (A), (B), and optionally (C).

[0139] Advantageously, the weights of product (A), product (B), and product (C) (encoded as [A], [B], and [C] respectively) are such that the ratio [B] / ([A]+[C]) is between 1.5 and 8, and the weights of products (A) and (B) are such that [C] ≤ [A].

[0140] For the ratio [B] / ([A]+[C]) to be favorable, it is between 2 and 7.

[0141] Non-crosslinked polyolefins The composition according to the present invention comprises at least one non-crosslinked polyolefin, which may be in the form of a phase dispersed in a matrix formed of semi-crystalline polyamide.

[0142] 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 alpha-olefin units, as defined above.

[0143] Advantageously, the composition comprises at least one crosslinked polyolefin as defined above and at least one uncrosslinked polyolefin as defined above.

[0144] In one embodiment, the alloy comprises at least one polyamide and a mixture of a polypropylene-based grafted polyolefin and a polypropylene-based non-grafted polyolefin.

[0145] polyamide: The at least one polyamide is selected from semicrystalline polyamides, amorphous polyamides, and mixtures thereof.

[0146] Advantageously, the at least one polyamide is selected from a single amorphous polyamide, a semicrystalline polyamide, and a mixture of two semicrystalline polyamides.

[0147] In the sense of the present invention, a semi-crystalline copolyamide refers to a polyamide having a glass transition temperature determined by DSC according to ISO standard 11357-3 2013, a melting temperature (Tm) determined by DSC according to ISO standard 11357-3 2013, and a crystallization enthalpy exceeding 30 J / g, preferably exceeding 40 J / g, during a cooling process at a rate of 20 K / min as measured by DSC according to ISO standard 11357-3 2013.

[0148] An amorphous polyamide, in the sense of the present invention, is a polyamide having only a glass transition temperature (not a melting temperature (Tm)) by DSC according to ISO standard 11357-2 of 2013, or a glass transition temperature by DSC according to ISO standard 11357-2 of 2013, and a crystallization enthalpy during the cooling process at a rate of 20 K / min in differential scanning calorimetry DSC measured according to ISO standard 11357-3 of 2013 is less than 30 J / g, particularly less than 20 J / g, preferably less than 15 J / g, indicating a polyamide having little crystallinity with a melting point.

[0149] The nomenclature used to define polyamides is described in ISO standard 1874-1 "Plastiques - Materiaux polyamides (PA) pour moulage et extrusion - Partie 1: Designation" of 2011, particularly on page 3 (Tables 1 and 2), and is well known to those skilled in the art.

[0150] In the first variant, the alloy consists of a single polyamide that is an amorphous polyamide and at least one polyolefin.

[0151] Amorphous polyamide: The amorphous polyamide can be a polyamide of formula A / XY, A is, at least one C₅ - C 12 , 12 , 12 , 10 , 12 , 18 , 36 , 10 , 18 , 10 , 12 , preferably C₆ - C 12 , more preferably C 10 - C 12 amino acid, or at least one C₅ - C 18 , preferably C₆ - C 12 , 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 12Aliphatic diamine Ca and at least one C4-C 36 Preferably C6~C 18 Preferably C6~C 12 , more preferably C8~C 12 It is an aliphatic repeating unit obtained by polycondensation of dicarboxylic acid Cb, XY is At least one alicyclic diamine, or at least one linear or branched aliphatic diamine X, and at least one aromatic dicarboxylic acid or at least one aliphatic dicarboxylic acid Y These are aliphatic repeating units obtained by polycondensation.

[0152] The amino acid is selected from 9-aminononanoic acid, 10-aminodecanoic acid, 10-aminoundecanoic acid, 12-aminododecanoic acid, and 11-aminoundecanoic acid, and their derivatives, and can be N-heptyl-11-aminoundecanoic acid, and especially 11-aminoundecanoic acid.

[0153] The lactam is selected from pyrrolidinene, 2-piperidinone, caprolactam, enantractam, capryloractam, pelargolactam, decanolactam, undecanolactam, and lauryllactam, and is particularly lauryllactam.

[0154] Said C4~C 36Aliphatic diamines Ca are linear or branched, and are particularly butanediamine, 1,5-pentamethyldiamine, 2-methyl-1,5-pentanediamine, 1,6-hexamethylenediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 2,2,4-trimethylhexamethylenediamine, and 2,4,4-trimethylhexamethylene Selected from diamines, 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-eicosanediamine, 1,22-docosanediamine, and fatty acid dimers.

[0155] Said C6~C 18 Aliphatic diamine Ca is linear or branched and is particularly selected from 1,6-hexamethylenediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 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, and 1,18-octadecanediamine.

[0156] Said C6~C 12 Aliphatic diamine Ca is linear or branched and is particularly selected from 1,6-hexamethylenediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,10-decanediamine, 1,11-undecanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, and 1,12-dodecanediamine.

[0157] Said C 10 ~C 12 Aliphatic diamine Ca is linear or branched, and is particularly selected from 1,10-decanediamine, 1,11-undecanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, and 1,12-dodecanediamine.

[0158] Said C4~C 36 Preferably C6~C 18 Preferably C6~C 12 , more preferably C8~C 12 Dicarboxylic acid Cb;

[0159] The C4-C36 dicarboxylic acid Cb is aliphatic and linear, and is particularly selected from succinic acid, pentanedioic acid, adipic acid, heptanedioic acid, suberic acid, azelaic acid and sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and docosanedioic acid.

[0160] Said C6~C 18 Dicarboxylic acid Cb is aliphatic and linear, and is particularly selected from adipic acid, heptanediic acid, suberic acid, azelaic acid and sebacic acid, undecanediic acid, dodecanediic acid, brassic acid, tetradecanediic acid, pentadecanediic acid, hexadecanedioic acid, and octadecanediic acid.

[0161] Said C6~C 12 Dicarboxylic acid Cb is aliphatic and linear, and is particularly selected from adipic acid, heptanediic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, and dodecanediic acid.

[0162] Above C8~C 12 Dicarboxylic acid Cb is aliphatic and linear, and is particularly selected from suberic acid, azelaic acid, sebacic acid, undecanediic acid, and dodecanediic acid.

[0163] In the aliphatic repeating unit XY, the diamine X may be an alicyclic diamine 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), isophorone diamine, piperazine, and amino-ethylpiperazine.

[0164] It may also contain the following carbon skeletons: norbornylmethane, cyclohexylmethane, dicyclohexylpropane, di(methylcyclohexyl), and di(methylcyclohexyl)propane. While not exhaustive, a list of these alicyclic diamines is provided in the publication "Cycloaliphatic Amines" (Encyclopaedia of Chemical Technology, Kirk-Othmer, 4th Edition (1992), pp. 386-405).

[0165] In the aliphatic repeating unit XY, the diamine X may be a linear or branched aliphatic diamine, selected from those defined above for diamine Ca.

[0166] In the aliphatic repeating unit XY, the diacid Y may be an aromatic dicarboxylic acid selected from terephthalic acid (denoted as T), isophthalic acid (denoted as I), and naphthalene diacid.

[0167] In the aliphatic repeating unit XY, the diacid Y can be an aliphatic dicarboxylic acid Y, selected from those defined above for diacid Cb.

[0168] It is clear that the units X and Y are different from the diamine units Ca and Cb.

[0169] To the advantage of A, at least one C5~C 18 Preferably C6~C 12 , more C 10 ~C 12 amino acids, or At least one C5~C 18 Preferably C6~C 12 , more C 10 ~C 12 These are aliphatic repeating units obtained by polycondensation of lactams.

[0170] Advantageously, XY is an aliphatic repeating unit obtained by polycondensation of at least one alicyclic diamine and at least one aromatic dicarboxylic acid or at least one aliphatic dicarboxylic acid Y.

[0171] To the advantage of A, at least one C5~C 18 Preferably C6~C 12 , more C 10 ~C 12 Amino acids, or at least one C5-C 18 Preferably C6~C 12 More preferably, the aliphatic repeating unit obtained by polycondensation of C10-C12 lactams, where XY is an aliphatic repeating unit obtained by polycondensation of at least one alicyclic diamine and at least one aromatic dicarboxylic acid or at least one aliphatic dicarboxylic acid Y.

[0172] To the advantage of the situation, A has at least one C. 10 ~C 12 Amino acids or at least one C 10 ~C 12 XY is an aliphatic repeating unit obtained by polycondensation of lactams, where XY is an aliphatic repeating unit obtained by polycondensation of at least one alicyclic diamine and at least one aromatic dicarboxylic acid or at least one aliphatic dicarboxylic acid Y.

[0173] Advantageously, the amorphous polyamide is selected from 11 / B10, 12 / B10, 11 / BI / BT, 11 / BI, and especially 11 / B10.

[0174] To the advantage of the situation, A has at least one C. 10 ~C 12 Amino acids or at least one C 10 ~C 12 XY is an aliphatic repeating unit obtained by polycondensation of lactams, where XY is an aliphatic repeating unit obtained by polycondensation of at least one alicyclic diamine and at least one aromatic dicarboxylic acid.

[0175] Advantageously, the amorphous polyamide is selected from 11 / BI / BT and 11 / BI.

[0176] To the advantage of the situation, A has at least one C. 10 ~C 12 Amino acids or at least one C 10 ~C 12 XY is an aliphatic repeating unit obtained by polycondensation of lactams, where XY is an aliphatic repeating unit obtained by polycondensation of at least one alicyclic diamine and at least one aliphatic dicarboxylic acid Y.

[0177] Advantageously, the amorphous polyamide is selected from 11 / B10, 12 / B10, and especially 11 / B10.

[0178] Advantageously, the alloy comprises a single polyamide which is an amorphous polyamide, and a mixture of polypropylene-based grafted polyolefins and polypropylene-based non-grafted polyolefins.

[0179] In the second modification, the alloy comprises a single semicrystalline polyamide or a mixture of two semicrystalline polyamides and at least one polyolefin.

[0180] Polyolefins are defined as described above.

[0181] Semicrystalline polyamide: Semicrystalline polyamides can be selected from aliphatic polyamides, particularly long-chain polyamides, aryl-aliphatic polyamides, and semi-aromatic polyamides.

[0182] The term "aliphatic polyamide" refers to homopolyamide or copolyamide. It is understood that it can be a mixture of aliphatic polyamides.

[0183] The term "long chain" means that the average number of carbon atoms per nitrogen atom is greater than 8, especially between 9 and 18.

[0184] In one embodiment, the polyamide mixture is a mixture of aliphatic polyamides, particularly long-chain polyamides, and aryl-aliphatic polyamides.

[0185] Aliphatic polyamides can be obtained by polycondensation of lactams, the lactam being selected from pyrrolidinone, 2-piperidinone, caprolactam, enantractam, caprylolactam, pelargolactam, decanolactam, undecanolactam, and lauryllactam, and in particular lauryllactam.

[0186] Aliphatic polyamides can also be obtained by polycondensation of amino acids, which can be selected from 9-aminononanoic acid, 10-aminodecanoic acid, 10-aminoundecanoic acid, 12-aminododecanoic acid, and 11-aminoundecanoic acid, as well as their derivatives, particularly N-heptyl-11-aminoundecanoic acid, and especially 11-aminoundecanoic acid.

[0187] Aliphatic polyamides can be obtained by polycondensation of units X1Y1, where X1 is a diamine and Y is a dicarboxylic acid.

[0188] X1 can be a linear or branched C5-C18 aliphatic diamine, and can be selected in particular from 1,5-pentamethyldiamine, 2-methyl-1,5-pentanediamine, 1,6-hexamethylenediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 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, and 1,18-octadecanediamine.

[0189] Advantageously, the diamine X1 used is C6-C12 and is particularly selected from butanediamine, pentanediamine, 2-methyl-1,5-pentanediamine, 1,6-hexamethylenediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,10-decanediamine, 1,11-undecanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, and 1,12-dodecanediamine.

[0190] Advantageously, the diamine X1 used is C10-C12, particularly selected from 1,10-decanediamine, 1,11-undecanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, and 1,12-dodecanediamine, and Y1 may be a C6-C18 aliphatic dicarboxylic acid, particularly C6-C12.

[0191] The C6-C18 aliphatic dicarboxylic acid Y1 can be selected from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, dodecanediic acid, brassic acid, tetradecanediic acid, pentadecanediic acid, hexadecanedioic acid, and octadecanediic acid.

[0192] The C6-C12 aliphatic dicarboxylic acid Y1 can be selected from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, and dodecanediic acid.

[0193] The C10-C12 aliphatic dicarboxylic acid Y1 can be selected from sebacic acid, undecanediic acid, and dodecanediic acid.

[0194] Advantageously, the aliphatic polyamide is selected from PA6, PA66, PA610, PA612, PA1010, PA1012, PA1212, PA11, and PA12, particularly PA1010, PA1012, PA1212, PA11, and PA12.

[0195] The term "aryl-aliphatic polyamide," as defined above, refers to a polyamide obtained by polycondensation of units X2Y1 (where X2 represents an aryldiamine and Y1 represents an aliphatic dicarboxylic acid).

[0196] The aryldiamine X2 may be selected from metaxylylenediamine (MXD) and paraxylylenediamine (PXD).

[0197] Advantageously, the aryl-aliphatic polyamide is selected from MXD6, MXD10, and MXD12.

[0198] Advantageously, the aryl-aliphatic polyamide is selected from MXD10 and MXD12.

[0199] Advantageously, the mixture of the two semicrystalline polyamides is a mixture of an aliphatic polyamide and an arylaliphatic polyamide.

[0200] Advantageously, the mixture of the two semicrystalline polyamides is a mixture of an aliphatic polyamide selected from PA6, PA66, PA610, PA612, PA1010, PA1012, PA1212, PA11, and PA12, particularly PA1010, PA1012, PA1212, PA11, and PA12, and an arylaliphatic polyamide selected from MXD6, MXD10, and MXD12.

[0201] Advantageously, the mixture of the two semicrystalline polyamides is a mixture of an aliphatic polyamide selected from PA1010, PA1012, PA1212, PA11, and PA12 and an arylaliphatic polyamide selected from MXD10 and MXD12.

[0202] The expression "semi-aromatic polyamide" means, in particular, a semi-aromatic polyamide of the formula described in European Patent No. 1505099, especially a semi-aromatic polyamide of formula B / ZT, where B is selected from a unit obtained by polycondensation of amino acids as defined above, a unit obtained by polycondensation of lactams as defined above, and a unit corresponding to formula X2Y2, where X2 and Y2 are defined above. ZT is a polyamide of Cx diamine and terephthalic acid, particularly polyamides of formula A / 6T, A / 9T, A / 10T, or A / 11T, especially polyamides PA6 / 6T, PA66 / 6T, PA6I / 6T, PA11 / 9T, PA11 / 10T, PA11 / 12T, PA12 / 9T, PA12 / 10T, PA12 / 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, PA11 / BACT / 10T, PA11 / MPMDT / 10T, and PA11 / MXDT / 10T are shown, as well as units obtained by polycondensation with block copolymers, particularly polyamide / polyether (PEBA), where x represents the number of carbon atoms in the Cx diamine, x is 4 to 36, preferably 6 to 18, preferably 6 to 12, preferably 10 to 12, and A is defined above.

[0203] T corresponds to terephthalic acid, MXD corresponds to m-xylenediamine, MPMD corresponds to methylpentamethylenediamine, and BAC corresponds to bis(aminomethyl)cyclohexane (1,3BAC and / or 1,4BAC).

[0204] Advantageously, the semi-aromatic polyamide is selected from PA11 / 9T, PA11 / 10T, PA11 / 12T, PA12 / 9T, PA12 / 10T, and PA12 / 12T.

[0205] Advantageously, the at least one polyamide is selected from a single amorphous polyamide, an aryl-aliphatic polyamide, an aliphatic polyamide, particularly a mixture of a long-chain polyamide and an aryl-aliphatic polyamide, and an aliphatic polyamide, particularly a mixture of a long-chain polyamide and a semi-aromatic polyamide.

[0206] Advantageously, the alloy comprises a mixture of two semicrystalline polyamides, and a mixture of polypropylene-based grafted polyolefins and polypropylene-based non-grafted polyolefins.

[0207] In one embodiment, the present invention relates to the use defined above, and the composition comprises an additive.

[0208] additives Additives may be present in amounts up to 2% by weight of the total weight of the composition, and in particular, they may be present in amounts of 1-2% by weight of the total weight of the composition.

[0209] Additives may be selected from among catalysts, antioxidants, heat stabilizers, UV stabilizers, light stabilizers, lubricants, flame retardants, nucleating agents, chain extenders, and colorants.

[0210] The term "catalyst" refers to polycondensation catalysts such as mineral acids or organic acids.

[0211] Advantageously, the weight proportion of the catalyst is approximately 50 ppm to approximately 5000 ppm, and particularly approximately 100 to approximately 3000 ppm, relative to the total weight of the composition.

[0212] Advantageously, the catalyst is selected from phosphoric acid (H3PO4), phosphorous acid (H3PO3), hypophosphorous acid (H3PO2), or a mixture thereof.

[0213] The antioxidant may be a copper complex-based antioxidant in particular at a concentration of 0.05 to 5% by weight, preferably 0.05 to 1% by weight, and preferably 0.1 to 1% by weight.

[0214] The term "copper complex" specifically refers to a complex between a monovalent or divalent copper salt containing an organic or inorganic acid and an organic ligand.

[0215] Advantageously, the copper salt can be selected from cupric (Cu(II)) salts of hydrogen halides, cuprous (Cu(I)) salts of hydrogen halides, and salts of aliphatic carboxylic acids.

[0216] In particular, copper salts are selected from CuCl, CuBr, CuI, CuCN, CuCl2, Cu(OAc)2, and copper stearate.

[0217] Copper complexes are described in particular in U.S. Patent No. 3,505,285.

[0218] The copper-based complex may further comprise ligands selected from phosphines, particularly triphenylphosphine, mercaptobenzimidazole, EDTA, acetylacetonate, glycine, ethylenediamine, oxalate, diethylenediamine, triethylenetetramine, pyridine, tetrabromobisphenyl-A, derivatives of tetrabisphenyl-A such as epoxy derivatives, and derivatives of chlorodimethanedibenzo(a,e)cyclooctene and mixtures thereof, diphosphones and dipyridyl or mixtures thereof, particularly triphenylphosphine and / or mercaptobenzimidazole.

[0219] The term "phosphine" refers to an alkylphosphine such as tributylphosphine, or an arylphosphine such as triphenylphosphine (TPP).

[0220] Advantageously, the ligand is triphenylphosphine.

[0221] Examples of complexes and methods for preparing them are described in Canadian Patent No. 02347258.

[0222] Advantageously, the amount of copper in the composition of the present invention is comprised of 10 ppm by weight to 1000 ppm by weight, particularly 20 ppm by weight to 70 ppm by weight, and particularly 50 to 150 ppm by weight, relative to the total weight of the composition.

[0223] Advantageously, the copper-based complex further comprises a halogenated organic compound.

[0224] The halogenated organic compound can be any halogenated organic compound.

[0225] Advantageously, the halogenated organic compound is a brominated compound and / or an aromatic compound.

[0226] Advantageously, the aromatic compound is selected from decabromodiphenyl, decabromodiphenyl ether, bromostyrene or chlorostyrene oligomer, and polydibromostyrene.

[0227] Advantageously, the halogenated organic compound is a brominated compound.

[0228] The halogenated organic compound is added to the composition in a halogen ratio of 50 to 30,000 ppm by weight, particularly 100 to 10,000 ppm, and especially 500 to 1,500 ppm by weight, relative to the total weight of the composition.

[0229] Advantageously, the molar ratio of copper to halogen is set to 1:1 to 1:3000, and especially 1:2 to 1:100.

[0230] In particular, the aforementioned ratios are composed of 1:1.5 to 1:15.

[0231] Copper complex-based antioxidants are advantageous.

[0232] The heat stabilizer may be an organic stabilizer, or more generally, a combination of organic stabilizers such as a first antioxidant of the phenolic type (e.g., Ciba's Irganox 245, 1098, or 1010 series), or a second antioxidant of the phosphate type.

[0233] UV stabilizers can be HALS, which means hindered amine light stabilizers or anti-UV (e.g., Ciba's Tinuvin 312).

[0234] The light stabilizer may be a hindered amine (e.g., Ciba's Tinuvin 770), a phenolic acid, or a phosphorus-based stabilizer.

[0235] The lubricant may be a fatty acid-based lubricant such as stearic acid.

[0236] The flame retardant may be a halogen-free flame retardant as described in U.S. Patent No. 2008 / 0274355, and in particular a phosphorus-based flame retardant, such as a metal salt of phosphinic acid, in particular a dialkylphosphinate salt, in particular aluminium diethylphosphinate or aluminium diethylphosphinate, a metal salt of diphosphinic acid, a mixture of an aluminum phosphinic acid flame retardant and a nitrogen synergist or a mixture of an aluminum phosphinic acid flame retardant and a phosphorus synergist, at least one metal salt of phosphinic acid, in particular an ammonium-based salt such as ammonium polyphosphate, ammonium sulfamate, or ammonium pentaborate, or a melamine-based salt such as melamine, melamine salts, melamine pyrophosphate, and melamine cyanurate, or a cyanuric acid-based salt, or at least one metal salt of diphosphinic acid or red phosphorus, a polymer containing a metal borate such as antimony oxide, zinc oxide, iron oxide, magnesium oxide, or zinc borate, or a mixture thereof. These may also be halogenated flame retardants such as brominated or polybrominated polystyrene, brominated polycarbonate, or brominated phenol.

[0237] The nucleating agent may be silica, alumina, clay, or talc, particularly talc.

[0238] Examples of suitable chain limiters include monoamines, monocarboxylic acids, diamines, triamines, dicarboxylic acids, tricarboxylic acids, tetraamines, tetracarboxylic acids, and oligoamines or oligocarboxylic acids having 5 to 8 amino or carboxyl groups, particularly dicarboxylic acids, in each case, as well as mixtures of tricarboxylic acids, tricarboxylic acids, or dicarboxylic acids. As an example, dodecanedicarboxylic acid can be used in the form of trimellitic acid as a dicarboxylic acid and tricarboxylic acid.

[0239] In other embodiments, with respect to the uses defined above, the composition comprises at least one prepolymer, in particular monofunctional NH2, in particular PA11 series.

[0240] Advantageously, the composition comprises a single prepolymer.

[0241] Prepolymer The prepolymer may be present in amounts up to 11% by weight of the total weight of the composition, and particularly in amounts of 0.1 to 11% by weight of the total weight of the composition.

[0242] Prepolymers are different from nucleating agents used as additives.

[0243] The term "prepolymer" refers to a polyamide oligomer that needs to have a lower number-average molecular weight than the polyamide used in the composition, and in particular, the number-average molecular weight of the prepolymer is 1,000 to 15,000 g / mol, and especially 1,000 to 10,000 g / mol.

[0244] The prepolymer may be selected from aliphatic linear or branched polyamide oligomers, alicyclic polyamide oligomers, semi-aromatic polyamide oligomers, aromatic polyamide oligomers, aliphatic linear or branched alicyclic semi-aromatic and aromatic polyamides, as defined above.

[0245] Therefore, the prepolymer or oligomer is derived from the following condensation: - At least one lactam, or - At least one amino acid, or - At least one diamine comprising at least one dicarboxylic acid, or a mixture thereof.

[0246] Therefore, the prepolymer or oligomer may not correspond to the condensation of a diamine containing a lactam or amino acid.

[0247] The prepolymer may also be a copolyamide oligomer, or a mixture of polyamide and copolyamide oligomer.

[0248] For example, the prepolymer may be monofunctional NH2, monofunctional CO2H, or difunctional CO2H or NH2.

[0249] Therefore, the prepolymer can be monofunctional or difunctional acid or amine, that is, if monofunctional, it has one terminal amine or acid function (in which case the other end is nonfunctional, in particular CH3), or if difunctional, it has two terminal amine functions or two terminal acid functions.

[0250] Advantageously, the prepolymer is monofunctional, preferably NH2 or CO2H.

[0251] It can also be non-functional at both ends, particularly at diCH3.

[0252] In one embodiment, the present invention, with respect to the use defined above, comprises the following compositions: The alloy consists of at least one polyamide and at least one polyolefin as defined above, in an amount of 30-70% by weight, particularly 35-60% by weight, and more particularly 40-50% by weight, with a polyamide / polyolefin ratio of 95 / 5-50 / 50; A mixture of solid and hollow glass strengthening agents as defined above, in an amount of 30-70% by weight, particularly 40-65% by weight, and more particularly 50-60% by weight; At least one prepolymer in 0–11% by weight, especially 0.1–11% by weight; Filler in 0-5% by weight and Additives should be 0-2% by weight, preferably 1-2% by weight. The sum of the proportions of each component in the aforementioned composition is equal to 100%.

[0253] In other embodiments, with respect to the use defined above, the present invention comprises the following compositions: The alloy consists of at least one polyamide and at least one polyolefin as defined above, in an amount of 30-70% by weight, particularly 35-60% by weight, and more particularly 40-50% by weight, with a polyamide / polyolefin ratio of 95 / 5-50 / 50; A mixture of solid and hollow glass strengthening agents as defined above in an amount of 30-70% by weight, particularly 40-65% by weight, and more particularly 50-60% by weight; and At least one prepolymer in 0–11% by weight, especially 0.1–11% by weight; Filler in 0-5% by weight and Additives should be 0-2% by weight, preferably 1-2% by weight. The sum of the proportions of each component in the aforementioned composition is equal to 100%.

[0254] In one embodiment, the present invention, with respect to the use defined above, comprises the following compositions: The alloy consists of at least one polyamide and at least one polyolefin as defined above, in an amount of 30-50% by weight, particularly 35-50% by weight, and more particularly 40-50% by weight, with a polyamide / polyolefin ratio of 95 / 5-50 / 50; A mixture of solid and hollow glass strengthening agents as defined above, in an amount of 50-70% by weight, particularly 50-65% by weight, and more particularly 50-60% by weight; At least one prepolymer in 0–11% by weight, especially 0.1–11% by weight; Filler in 0-5% by weight and Additives should be 0-2% by weight, preferably 1-2% by weight. The sum of the proportions of each component in the aforementioned composition is equal to 100%.

[0255] In yet another embodiment, with respect to the use defined above, the composition of the present invention is as follows: The alloy consists of at least one polyamide and at least one polyolefin as defined above, in an amount of 30-50% by weight, particularly 35-50% by weight, and more particularly 40-50% by weight, with a polyamide / polyolefin ratio of 95 / 5-50 / 50; A mixture of solid and hollow glass strengthening agents as defined above in an amount of 50-70% by weight, particularly 50-65% by weight, and more particularly 50-60% by weight; and At least one prepolymer in 0–11% by weight, especially 0.1–11% by weight; Filler in 0-5% by weight and Additives should be 0-2% by weight, preferably 1-2% by weight. The sum of the proportions of each component in the aforementioned composition is equal to 100%.

[0256] In other embodiments, the present invention relates particularly to compositions useful for injection molding, and includes the following: The alloy consists of at least one polyamide and at least one polyolefin as defined above, in an amount of 30-70% by weight, particularly 35-60% by weight, and more particularly 40-50% by weight, with a polyamide / polyolefin ratio of 95 / 5-50 / 50; A mixture of solid and hollow glass strengthening agents as defined above in an amount of 30-70% by weight, particularly 40-65% by weight, and more particularly 50-60% by weight; and At least one prepolymer in 0–11% by weight, especially 0.1–11% by weight; Filler in 0-5% by weight and Additives should be 0-2, preferably 1-2% by weight. The sum of the proportions of each component in the aforementioned composition is equal to 100%.

[0257] Advantageously, the composition is particularly useful for injection molding and consists of the following: The alloy consists of at least one polyamide and at least one polyolefin as defined above, in an amount of 30-70% by weight, particularly 35-60% by weight, and more particularly 40-50% by weight, with a polyamide / polyolefin ratio of 95 / 5-50 / 50; A mixture of solid and hollow glass reinforcing agents defined above is 30 to 70% by weight, particularly 40 to 65% by weight, more particularly 50 to 60% by weight; and At least one prepolymer is 0 to 11% by weight, particularly 0.1 to 11% by weight; The filler is 0 to 5% and The additive is 0 to 2, preferably 1 to 2% by weight, The sum of the proportions of the components of the composition is equal to 100%.

[0258] In one embodiment, the composition is particularly useful for injection molding and comprises: An alloy consisting of at least one polyamide and at least one polyolefin defined above is 30 to 50% by weight, particularly 35 to 50% by weight, more particularly 40 to 50% by weight, and the polyamide / polyolefin ratio is 95 / 5 to 50 / 50; A mixture of solid and hollow glass reinforcing agents defined above is 50 to 70% by weight, particularly 50 to 65% by weight, more particularly 50 to 60% by weight; and At least one prepolymer is 0 to 11% by weight, particularly 0.1 to 11% by weight; The filler is 0 to 5% and The additive is 0 to 2% by weight, preferably 1 to 2% by weight, The sum of the proportions of the components of the composition is equal to 100%.

[0259] In another embodiment, the composition is particularly useful for injection molding and consists of: An alloy consisting of at least one polyamide and at least one polyolefin defined above is 30 to 50% by weight, particularly 35 to 50% by weight, more particularly 40 to 50% by weight, and the polyamide / polyolefin ratio is 95 / 5 to 50 / 50; A mixture of solid and hollow glass reinforcing agents defined above is 50 to 70% by weight, particularly 50 to 65% by weight, more particularly 50 to 60% by weight; and At least one prepolymer is 0 to 11% by weight, particularly 0.1 to 11% by weight; The filler is 0 to 5% and The additive is 0 to 2% by weight, preferably 1 to 2% by weight, The sum of the proportions of each component in the aforementioned composition is equal to 100%.

[0260] In one embodiment, the composition does not contain polyamides 6 and 66.

[0261] All the properties defined above for the use defined above are effective in the composition as such.

[0262] About fillers The composition may also contain fillers. Possible fillers include pigments such as kaolin, magnesia, slag, carbon black, expanded or non-expanded graphite, wollastonite, titanium oxide, and zinc sulfide, and conventional inorganic fillers such as antistatic fillers.

[0263] Advantageously, the composition is particularly useful for injection molding and consists of the following: The alloy consists of at least one polyamide and at least one polyolefin as defined above, in an amount of 30-70% by weight, particularly 35-60% by weight, and more particularly 40-50% by weight, with a polyamide / polyolefin ratio of 95 / 5-50 / 50; A mixture of solid and hollow glass strengthening agents as defined above in an amount of 30-70% by weight, particularly 40-65% by weight, and more particularly 50-60% by weight; and At least one prepolymer in 0–11% by weight, especially 0.1–11% by weight; The filler is 0-5% by weight, and Additives should be 0-2% by weight, preferably 1-2% by weight. The sum of the proportions of each component in the aforementioned composition is equal to 100%.

[0264] In other embodiments, the present invention relates to the use of the compositions defined above for the manufacture of articles, particularly for electronics, telecommunications, or data exchange, such as for autonomous vehicles or for interconnected applications.

[0265] Advantageously, the article is manufactured by injection molding.

[0266] Stated otherwise, the present invention relates to a method for preparing articles for autonomous vehicles or interconnection applications, etc., particularly for electronics, telecommunications applications, or data exchange, etc., including the process of the above-defined composition, particularly by injection molding.

[0267] According to another aspect, the present invention relates to an article obtained by injection molding of the above-defined composition.

Examples

[0268] Hereinafter, the present invention will be further specifically described by the following examples without being limited to these examples.

[0269] Various polyamides and copolyamides of the present invention were prepared according to the usual techniques for the synthesis of polyamides and copolyamides.

[0270] Synthesis of CoPa11 / 10T, a representative of various copolyamides: Aminoundecane, decanediamine, and terephthalic acid monomers are loaded together into a reaction vessel according to the desired mass ratio. First, the medium is inactivated to remove oxygen that may cause yellowing or secondary reactions. It is also possible to fill with water to improve heat exchange. Two temperature rises and pressure plateaus are performed. The temperature (T°) and pressure conditions are selected such that the medium can be melted. After reaching the maintenance conditions, degassing is performed to enable the polycondensation reaction. The medium gradually becomes viscous, and nitrogen purge and vacuum are applied to form the reaction water. When the stop conditions are reached and related to the desired viscosity, stirring can be stopped, and extrusion and granulation can be started.

[0271] The compositions in Table 1 were prepared according to the following general protocol (wt%):

[0272] Formulation for the preparation of granules of the above formulation: A twin-screw extruder such as Coperion ZSK 26 MC equipped with at least one outer raw material inlet Machine temperature: 270°C Screw speed: 250 rpm Extruder extrusion rate: 16 kg / h

[0273] Transformation: A 100x100x2mm³ wafer was manufactured by injection molding, and its dielectric properties were measured. The following parameters were used: -ENGEL VICTORY500, 160T hydraulic press - Injection temperature (supply / nozzle): 265°C / 280°C - Mold temperature: 100°C -Holding time: 10s -Material holding pressure: 700 bar -Cooling time: 35s

[0274] Dumbbell-shaped test specimens were manufactured by injection molding according to ISO 527-21A for the measurement of tensile mechanical properties. The following parameters were used: -ENGEL VICTORY500, 160T hydraulic press - Injection temperature (supply / nozzle): 285°C / 295°C - Mold temperature: 100°C -Holding time: 10s -Material holding pressure: 700 bar - Cooling time: 15s

[0275] The results obtained from the compositions of the present invention are shown in Tables 1 and 2 below: TIFF2022536159000001.tif128170TIFF2022536159000002.tif107170

[0276] The comparative compositions are shown in Table 3 below: TIFF2022536159000003.tif124170I1~I9: Invention 1~9 C1~C13: Comparative composition C1~C13 N / A: Not tested PA11: Rilsan (Arkema) PA11 / 10T (weight: 28 / 72) PA11 / B10 (10 / 90 by weight) Polypropylene PPH5060: Non-grafted polypropylene homopolymer from whole Orevac CA100: Maleic anhydride grafted polypropylene (Arkema) PA Dual: PA11 Mono NH2

[0277] The term "antioxidant" refers specifically to phenolic antioxidants.

[0278] The second type of antioxidant corresponds to phosphite antioxidants. NE glass fiber: NE solid glass fiber with a flattened cross-section, manufactured by Nitto Boseki Co., Ltd. E-glass fiber: Solid E-glass fiber with a circular cross-section, manufactured by Nitto Boseki or Nippon Electric Glass Co., Ltd. HM Glass Fiber: A solid fiber with a circular cross-section manufactured by AGY Corporation (high modulus glass fiber). Glass beads: Hollowlite glass beads Dk and tan delta are measured in accordance with ASTM D-2520-13.

[0279] The tensile modulus (or modulus of elasticity E) is measured according to ISO 527-1 and 527-2 of 2012.

Claims

1. Use of a mixture of solid and hollow glass reinforcing agents with an alloy consisting of at least one polyamide and at least one polyolefin, wherein the mixture of solid and hollow glass reinforcing agents contains 5 to 50% by weight of hollow glass beads based on the total of solid and hollow glass reinforcing agents, and the mixture of solid and hollow glass reinforcing agents contains, in addition to the hollow glass beads, solid glass fibers selected from circular cross-section glass fibers, flat cross-section glass fibers, and mixtures thereof, except for polyamides 6 and 66, for preparing a composition having a dry modulus of elasticity equal to at least 8 GPa at 23 °C, a dielectric constant Dk of 3.5 or less measured at a frequency of at least 1 GHz, 23 °C, and 50% RH in accordance with ASTM D-2520-13, and a dielectric loss (tan delta) of 0.01 or less measured on a dry sample at a frequency of at least 1 GHz at 23 °C and 50% RH in accordance with ASTM D-2520-13.

2. The use according to claim 1, wherein the mixture of solid and hollow glass reinforcing agents contains 5 to 35% by weight of hollow glass beads based on the total of solid and hollow glass reinforcing agents.

3. The use according to claim 1 or 2, wherein the composition has a modulus of elasticity equal to at least 10 GPa.

4. The use according to claim 1 or 2, wherein the composition has a modulus of elasticity equal to at least 11 GPa.

5. The use according to any one of claims 1 to 4, wherein the composition has a dielectric constant Dk of 3.3 or less.

6. The use according to any one of claims 1 to 4, wherein the composition has a dielectric constant Dk of 3.2 or less.

7. The use according to any one of claims 1 to 6, wherein the composition is measured at a frequency of at least 2 GHz in accordance with ASTM D-2520-13.

8. The use according to any one of claims 1 to 6, wherein the composition is measured at a frequency of at least 3 GHz in accordance with ASTM D-2520-13.

9. The use according to any one of claims 1 to 7, wherein the dielectric loss (tan delta) of the composition is 0.01 or less measured on a dry sample at a frequency up to 2.4 GHz at 23 °C and 50% RH in accordance with ASTM D-2520-13.

10. The mixture of the glass reinforcing agent is used according to any one of claims 1 to 9, and consists of 50 to 95% by weight of solid glass fibers and 5 to 50% by weight of hollow glass beads.

11. The mixture of the glass reinforcing agent is used according to any one of claims 1 to 9, and consists of 65 to 95% by weight of solid glass fibers and 5 to 35% by weight of hollow glass beads.

12. The alloy consists of at least one polyamide and at least one polyolefin, and the polyamide / polyolefin weight ratio is 95 / 5 to 50 / 50. The use is as described in any one of claims 1 to 11.

13. The at least one polyolefin is selected from graft polyolefins, non-grafted polyolefins, and mixtures thereof. The use is as described in any one of claims 1 to 12.

14. The reaction unit of the graft polyolefin is selected from esters of unsaturated carboxylic acids. The use is as described in claim 13.

15. The graft polyolefin is propylene-based. The use is as described in claim 13 or 14.

16. 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. The use is as described in claim 13.

17. The non-grafted polyolefin is selected from propylene, ethylene, or diene. The use is as described in claim 13.

18. The non-grafted polyolefin is propylene-based. The use is as described in any one of claims 13, 16, and 17.

19. The alloy consists of at least one polyamide and a mixture of a polypropylene-based graft polyolefin and a polypropylene-based non-grafted polyolefin. The use is as described in any one of claims 12 to 18.

20. The at least one polyamide is selected from semi-crystalline polyamides, amorphous polyamides, and mixtures thereof. The use is as described in any one of claims 1 to 19.

21. The use according to any one of claims 1 to 20, wherein the alloy consists of a single polyamide that is an amorphous polyamide and at least one polyolefin.

22. The amorphous polyamide is a polyamide of the formula A / XY, wherein, A is, At least one C ６ - C １８ amino acid, or At least one C ６ to C １８ lactam, or At least one C ４ - C ３６ An aliphatic diamine Ca and at least one C ４ - C ３６ An aliphatic repeating unit obtained by polycondensation of a dicarboxylic acid Cb, XY is, an aliphatic repeating unit obtained by polycondensation of at least one alicyclic diamine or at least one linear or branched aliphatic diamine X and at least one aromatic dicarboxylic acid or at least one aliphatic dicarboxylic acid Y, the use according to claim 21.

23. The amino acid in Ca is at least one C １０ to C １２ amino acid, and the use according to claim 22.

24. The lactam in Ca is at least one C １０ ~C １２ lactam, the use according to claim 22 or 23.

25. The aliphatic diamine in Ca is at least one C １０ -C １２ Use according to any one of claims 22 to 24, which is an aliphatic diamine.

26. Cb is at least one C ８ ~C １２ The use according to any one of claims 22 to 25, which is a dicarboxylic acid.

27. The amorphous polyamide is selected from 11 / B10, 12 / B10, 11 / BI / BT, 11 / BI, the use according to any one of claims 21 to 26.

28. The use according to any one of claims 1 to 20, wherein the alloy consists of a single semi-crystalline polyamide or a mixture of two semi-crystalline polyamides and at least one polyolefin.

29. The semi-crystalline polyamide is selected from aliphatic polyamides, aryl-aliphatic polyamides, and semi-aromatic polyamides, the use according to claim 28.

30. The mixture of polyamides is a mixture of an aliphatic polyamide and an aryl-aliphatic polyamide, the use according to claim 28 or 29.

31. The aliphatic polyamide is selected from PA610, PA612, PA1010, PA1012, PA1212, PA11, and PA12, the use according to claim 29 or 30.

32. The aliphatic polyamide is selected from PA1010, PA1012, PA1212, PA11, PA12, the use according to claim 29 or 30.

33. The aryl-aliphatic polyamide is selected from MXD6, MXD10, MXD12, the use according to claim 29 or 30.

34. The semi-aromatic polyamide is selected from PA11 / 9T, PA11 / 10T, PA11 / 12T, PA12 / 9T, PA12 / 10T, PA12 / 12T, the use according to claim 29.

35. The use according to any one of claims 19 to 27, wherein the alloy consists of a single polyamide that is an amorphous polyamide and a mixture of a polypropylene-based graft polyolefin and a polypropylene-based non-grafted polyolefin.

36. The use according to any one of claims 19 and 28 to 34, wherein the alloy consists of a mixture of two semi-crystalline polyamides and a mixture of a polypropylene-based graft polyolefin and a polypropylene-based non-grafted polyolefin.

37. The use according to any one of claims 1 to 36, wherein the composition contains an additive.

38. The use according to any one of claims 1 to 37, wherein the composition contains at least one prepolymer.

39. An alloy consisting of at least one polyamide and at least one polyolefin according to any one of claims 1 to 36, with a polyamide / polyolefin ratio of 95 / 5 to 50 / 50, 30 to 70% by weight; Containing 30 to 70% by weight of a mixture of solid and hollow glass reinforcing agents according to any one of claims 1 to 36; Except for polyamide 6 and 66, 0 to 11% by weight of at least one prepolymer; 0 to 5% by weight of a filler, and 0 to 2% by weight of an additive, The composition in which the sum of the proportions of the components of the composition is equal to 100%.

40. A composition useful for injection molding, An alloy consisting of at least one polyamide and at least one polyolefin according to any one of claims 1 to 36, with a polyamide / polyolefin ratio of 95 / 5 to 50 / 50, 30 to 70% by weight; Containing 30 to 70% by weight of a mixture of solid and hollow glass reinforcing agents according to any one of claims 1 to 36; Except for polyamide 6 and 66, 0 to 11% by weight of at least one prepolymer; 0 to 5% by weight of a filler, and 0 to 2% by weight of an additive, The composition in which the sum of the proportions of the components of the composition is equal to 100%.

41. The composition according to claim 39 or 40, containing 35 to 60% by weight of an alloy consisting of at least one polyamide and at least one polyolefin according to any one of claims 1 to 36, with a polyamide / polyolefin ratio of 95 / 5 to 50 / 50.

42. The composition according to claim 39 or 40, containing 40 to 50% by weight of an alloy consisting of at least one polyamide and at least one polyolefin according to any one of claims 1 to 36, with a polyamide / polyolefin ratio of 95 / 5 to 50 / 50.

43. A composition according to any one of claims 39 to 42, comprising 40 to 65% by weight of a mixture of solid and hollow glass reinforcing agents as claimed in any one of claims 1 to 36.

44. A composition according to any one of claims 39 to 42, comprising 50 to 60% by weight of a mixture of solid and hollow glass reinforcing agents as claimed in any one of claims 1 to 36.

45. A composition according to any one of claims 39 to 44, comprising 0.1 to 11% by weight of at least one prepolymer.

46. A composition according to any one of claims 39 to 45, comprising 1 to 2% by weight of an additive.

47. Use of a composition according to any one of claims 1 to 38 for the manufacture of an article.

48. Use of a composition according to any one of claims 1 to 38 for the manufacture of an article for electronics, for telecommunications applications, or for data exchange.

49. Use according to claim 47 or 48, characterized in that the article is manufactured by injection molding.

50. An article obtained by injection molding of a composition according to any one of claims 1 to 38.