阅读说明：本技术 包含增强纤维的具有高模量稳定性的共聚酰胺组合物及其用途 (Copolyamide composition with high modulus stability comprising reinforcing fibers and use thereof ) 是由 M.萨巴德 B.布鲁尔 M.波米尔德桑蒂 S.卡西亚诺加斯帕 D.维特里 R.毛 于 2020-03-13 设计创作，主要内容包括：本发明涉及式A/X-(1)Y的包含至少两种单元的共聚酰胺用以制备组合物的用途,其中：A是通过以下的缩聚获得的重复单元：至少一种C-(9)-C-(18)、优选地C-(10)-C-(18)、更优选地C-(10)-C-(12)氨基酸,或至少一种C-(9)-C-(18)、优选地C-(10)-C-(18)、更优选地C-(10)-C-(12)内酰胺,或至少一种C-(4)-C-(36)、优选地C-(6)-C-(18)、优选地C-(6)-C-(18)、更优选地C-(10)-C-(18)二胺Ca与至少一种C-(4)-C-(36)、优选地C-(6)-C-(18)、优选地C-(6)-C-(18)、更优选地C-(10)-C-(18)二酸Cb；X-(1)Y是得自至少一种C-(4)-C-(8)、优选地C-(4)-C-(6)、更优选地C-(6)线性脂族二胺(X-(1))和至少一种芳族二羧酸(Y)的缩聚的重复单元,所述组合物包含相对于组合物的总重量计的30-70％重量的增强纤维,并且该组合物的模量在20℃至40℃的温度范围中、特别是在0℃至40℃的温度范围中、更特别是在-10℃至40℃的温度范围中变化不超过20％。本发明还涉及包含这样的共聚酰胺的组合物、用于制造之的方法和可由其获得的模塑制品。(The invention relates to the formula A/X 1 Use of a copolyamide of Y comprising at least two units for the preparation of a composition, wherein: a is a repeating unit obtained by polycondensation of: at least one C 9 ‑C 18 Preferably C 10 ‑C 18 More preferably C 10 ‑C 12 Amino acid, or at least one C 9 ‑C 18 Preferably C 10 ‑C 18 More preferably C 10 ‑C 12 Lactams, or at least one C 4 ‑C 36 Preferably C 6 ‑C 18 Preferably C 6 ‑C 18 More preferably C 10 ‑C 18 Diamine Ca and at least one C 4 ‑C 36 Preferably C 6 ‑C 18 Preferably C 6 ‑C 18 More preferably C 10 ‑C 18 A diacid Cb; x 1 Y is derived from at least one C 4 ‑C 8 Preferably C 4 ‑C 6 More preferably C 6 Linear aliphatic diamine (X) 1 ) And at least one aromatic dicarboxylic acid (Y), the composition comprising 30-70% by weight of reinforcing fibers relative to the total weight of the composition, and the modulus of the composition not varying more than 20% in the temperature range of 20 ℃ to 40 ℃, in particular in the temperature range of 0 ℃ to 40 ℃, more in particular in the temperature range of-10 ℃ to 40 ℃. The invention also relates to compositions comprising such copolyamides, to a process for the manufacture thereof and to moulded articles obtainable therefrom.)

1. Formula A/X₁Y comprising at least two different unitsA and X₁Use of a copolyamide of Y for the preparation of a composition in which:

-a is a repeating unit obtained by polycondensation of:

at least one C₉-C₁₈Preferably C₁₀-C₁₈More preferably C₁₀-C₁₂An amino acid, or

At least one C₉-C₁₈Preferably C₁₀-C₁₈More preferably C₁₀-C₁₂Lactam, or

At least one C₄-C₃₆Preferably C₆-C₁₈Preferably C₆-C₁₂More preferably C₁₀-C₁₂Ca diamine and at least one C₄-C₃₆Preferably C₆-C₁₈Preferably C₆-C₁₂More preferably C₁₀-C₁₂A (B) dicarboxylic acid,

the at least one Ca diamine is a linear or branched aliphatic diamine and the at least one Cb diacid is a linear or branched aliphatic diacid,

66/6T copolyamides are excluded;

-X₁y is a radical of at least one C₄-C₈Preferably C₄-C₆More preferably C₆Linear aliphatic diamine (X)₁) And at least one aromatic dicarboxylic acid (Y),

the composition comprises 30-70% by weight of reinforcing fibers relative to the total weight of the composition and the modulus of the composition does not vary by more than 20% in a temperature range of 20 ℃ to 40 ℃, in particular in a temperature range of 0 ℃ to 40 ℃, in particular in a temperature range of-10 ℃ to 40 ℃.

2. Use according to claim 1, wherein X₁Y is through at least one C₄-C₈Preferably C₄-C₆More preferably C₆Aliphatic diamine (X)₁) And at least one aromatic dicarboxylic acid (Y).

3. Use according to one of claims 1 or 2, wherein Y is terephthalic acid.

4. Use according to one of claims 1 to 3, wherein X₁Y is a unit selected from units 4T, 6T and mixtures thereof, preferably 6T.

5. Use according to one of claims 1 to 4, wherein in the reaction mixture having the formula A/X₁In the copolyamide of Y, A is an amino acid or a lactam.

6. Use according to one of claims 1 to 5, wherein in the reaction mixture having the formula A/X₁In the copolyamide of Y, A is C₁₁Or C₁₂An amino acid or a lactam.

7. Use according to any one of claims 1 to 6, wherein the copolyamide is semi-crystalline, in particular having an enthalpy of crystallization higher than 30J/g.

8. Use according to any one of claims 1 to 7, wherein the copolyamide is of formula A/X only₁Units A and X of Y₁And Y is the same as the formula.

9. Use according to one of claims 1 to 7, wherein the copolyamide comprises at least one of A and X₁A third unit Z which is different from the unit Y and corresponds to the formula A/X₁Y/Z

Wherein:

units A and X₁Y is as defined in claim 1,

z is selected from the group consisting of units derived from amino acids, units derived from lactams and units having the formula (Cc diamine) (Cd diacid), wherein c represents the number of carbon atoms in the diamine and d represents the number of carbon atoms in the diacid, c and d each being from 4 to 36, advantageously from 9 to 18,

with the proviso that caprolactam or aminocaproic acid is excluded from the definition of lactam and amino acid of Z, and terephthalic acid is excluded from the definition of Cd diacid when Cc diamine is C10 diamine.

10. Use according to claim 9, wherein the copolyamide is of formula A/X only₁Three units of Y/Z.

11. Use according to one of claims 1 to 10, wherein the composition comprises 30 to 70% by weight of reinforcing fibres.

12. Use according to claim 11, wherein the reinforcing fibres are selected from glass fibres and carbon fibres or mixtures thereof, in particular glass fibres.

13. A composition, particularly useful for injection molding, comprising:

35 to 70%, in particular 35 to 50%, and more particularly 38 to 50% by weight of at least one copolyamide as defined in one of claims 1 to 12,

-30-70% by weight of reinforcing fibres;

-0-10% by weight of at least one impact modifier;

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

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

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

provided that when the reinforcing fiber is non-circular in cross section and has a cross section of 1.5 to 5.0X 10^-6cm²At a cross-sectional area of not more than 1.75, in particular 1.6, by weight of reinforcing fibres to copolyamide;

the sum of the proportions of the ingredients of the composition is equal to 100%.

14. The composition according to claim 13, wherein the copolyamide is selected from the group consisting of PA11/4T, PA11/6T, PA12/4T, PA12/6T, PA1010/4T, PA1012/4T, PA1010/6T, PA1012/6T, PA1210/4T, PA1212/4T, PA1210/6T, PA1212/6T, in particular PA 11/6T.

15. The composition according to claim 13 or 14, wherein the reinforcing fibers are selected from glass fibers, carbon fibers and mixtures thereof, in particular glass fibers.

16. The composition according to claim 15, wherein the glass fibers are selected from the group consisting of glass fibers of non-circular cross-section and glass fibers of circular cross-section, carbon fibers and mixtures thereof, in particular glass fibers of non-circular cross-section and glass fibers of circular cross-section and mixtures thereof, in particular glass fibers of non-circular cross-section.

17. Method for manufacturing a composition as defined in claims 13-16, wherein the ingredients of the composition are mixed by compounding, in particular in a twin-screw extruder, blender or internal mixer.

18. A molded article obtainable by injection molding from the composition according to any one of claims 13 to 16.

19. The molded article according to claim 18, which is used in electrical and electronic applications and is selected in particular from television sets, digital cameras, digital game machines, telephone parts, digital tablets, drones, printers or computer parts.

Technical Field

The present patent application relates to the use of semi-aromatic copolyamides for the manufacture of compositions having high modulus stability under the influence of temperature and humidity, to the process for their manufacture and to said compositions.

Background

Many applications in the E/E field require the use of high modulus polymeric materials, for example for televisions, digital cameras, digital games, telephone parts, digital tablets, drones, printers or computer parts. The modulus of the material is indeed a key factor allowing a lower weight, since it enables a reduction in the thickness of the component while maintaining a high rigidity. A distinction is made between different moduli (e.g., tensile modulus, flexural modulus, etc.). These moduli can be affected by the moisture level and temperature of the sample.

It is also important that the stiffness is hardly affected by the water content or temperature changes of the material. Indeed, modulus stability is also an important factor for subsequent use or to ensure that components are easily assembled (when such assembly is carried out where temperature and/or humidity can be high).

It is therefore desirable to find polymers whose modulus remains stable in the temperature and/or humidity range to which they are exposed, especially during component assembly and subsequent operation of the equipment. Preferably, the modulus is stable at temperatures of 20 ℃ to 40 ℃, in particular in the temperature range of 0 ℃ to 40 ℃, in particular in the temperature range of-10 ℃ to 40 ℃, for compositions having different water contents resulting from conditioning (conditioning) the composition in an atmosphere whose humidity may be 0-100%, or in liquid water.

Furthermore, the polymer formulation must have a moderate molding temperature and crystallize quickly enough to allow processing times, especially cycle times, to be suitable for use in industrial processes.

However, aliphatic polyamides generally undergo a significant loss of rigidity when the temperature is raised, in particular when these polyamides have been conditioned beforehand in a humid atmosphere, since they contain a certain amount of water.

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

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

Furthermore, document WO 10/015785 describes a copolyamide comprising at least two different a/X.T units, characterized in that the copolyamide has an amine chain end content of greater than or equal to 20 μ eq/g, a chain end content of less than or equal to 100 μ eq/g and a non-reactive chain end content of greater than or equal to 20 μ eq/g. The copolyamide may contain additives, in particular reinforcing fibers, which may be glass fibers.

Document WO 10/015786 describes a copolyamide comprising at least two a/10.T units, characterized in that it has a polydispersity index, expressed as Ip, lower than or equal to 3.5, measured by gel permeation chromatography.

International application WO 2014/195226 describes a composition for use in electronic mobile devices, the composition comprising at least 20% of at least one polymer and at least 20% of glass fibers having a non-circular cross-section and an elastic modulus of at least 76GPa, as determined in accordance with ASTM C1557-03.

None of these prior art documents mentions the stability of the modulus as a function of temperature and preconditioning of the composition.

This leaves the problem of providing polyamide-based formulations that combine high modulus, which is stable over a wide temperature range, even when the composition is saturated with water, with good injection moldability.

Disclosure of Invention

It is therefore an object of the present invention to provide semi-aromatic copolyamides for making compositions having high modulus stability under hardness in temperature and humidity.

Thus, according to a first aspect, the object of the invention is a compound of formula A/X₁Y comprises at least two differentUnits A and X₁Use of a copolyamide of Y for the preparation of a composition in which:

-a is a repeating unit obtained by polycondensation of:

at least one C₉-C₁₈Preferably C₁₀-C₁₈More preferably C₁₀-C₁₂An amino acid, or

At least one C₉-C₁₈Preferably C₁₀-C₁₈More preferably C₁₀-C₁₂Lactam, or

At least one C₄-C₃₆Preferably C₆-C₁₈Preferably C₆-C₁₂More preferably C₁₀-C₁₂Ca diamine and at least one C₄-C₃₆Preferably C₆-C₁₈Preferably C₆-C₁₂More preferably C₁₀-C₁₂Cb dicarboxylic acid;

-X₁y is a radical of at least one C₄-C₈Preferably C₄-C₆More preferably C₆Linear aliphatic diamine (X)₁) And at least one aromatic dicarboxylic acid (Y),

the modulus of the composition does not vary by more than 20% in the temperature range of 20 ℃ to 40 ℃, in particular in the temperature range of 0 ℃ to 40 ℃, in particular in the temperature range of-10 ℃ to 40 ℃.

In other words, it is an object of the present invention to use the formula A/X as defined hereinbefore₁Y comprising at least two different units A and X₁The copolyamide of Y is used to prepare a composition whose modulus does not change by more than 20% in the temperature range of 20 ℃ to 40 ℃, in particular in the temperature range of 0 ℃ to 40 ℃, especially in the temperature range of-10 ℃ to 40 ℃, compared to the change in modulus of the aliphatic homopolyamide measured under the same conditions.

Or, in other words, the object of the invention is to use the formula A/X as defined above₁Y comprising at least two different units A and X₁Copolyamides of Y for the preparation of combinationsThe modulus of the composition does not vary by more than 20% in the temperature range from 20 ℃ to 40 ℃, in particular in the temperature range from 0 ℃ to 40 ℃, in particular in the temperature range from-10 ℃ to 40 ℃, compared to the variation in modulus of an aliphatic homopolyamide having the same unit A, measured under the same conditions.

Or, in other words, the object of the invention is to use a composition comprising formula A/X as defined above₁Y comprising at least two different units A and X₁Y, to limit the variation in modulus in the temperature range from 20 ℃ to 40 ℃, in particular in the temperature range from 0 ℃ to 40 ℃, in particular in the temperature range from-10 ℃ to 40 ℃, by not more than 20% compared with the variation in modulus of the composition measured under the same conditions in which an aliphatic homopolyamide is used instead of the copolyamide.

Or, in other words, the object of the invention is to use a composition comprising formula A/X as defined above₁Y comprising at least two different units A and X₁Y, to limit the variation in modulus in the temperature range from 20 ℃ to 40 ℃, in particular in the temperature range from 0 ℃ to 40 ℃, in particular in the temperature range from-10 ℃ to 40 ℃, by not more than 20% compared with the variation in modulus of the composition measured under the same conditions in which an aliphatic homopolyamide having the same units A is used instead of the copolyamide.

Unexpectedly, the inventors have found that the selection comprises repeating units X based on aromatic diacids₁The semi-aromatic copolyamide of Y and of the repeating unit a makes it possible to prepare the following compositions: its modulus not only exhibits stability under the influence of temperature and humidity and does not change by more than 20% in the temperature range from 20 ℃ to 40 ℃, in particular in the temperature range from 0 ℃ to 40 ℃, in particular in the temperature range from-10 ℃ to 40 ℃, but also its processing is promoted by low molding temperatures, in particular low molding temperatures below 100 ℃, preferably below 90 ℃, and by short cycle times during its processing.

The nomenclature used to define polyamides is described in ISO Standard 1874-1:2011 "plastics-Material Polyamides (PA) pore molecular et exclusion-Partie 1: Designation", in particular on page three (tables 1 and 2), and is well known to the person skilled in the art.

In one embodiment, copolyamide 66/6T is excluded from the definition of copolyamide a/XT of the present invention.

In one embodiment, the at least one Ca diamine is C₇-C₁₈Preferably C₇-C₁₂More preferably C₁₀-C₁₂And said at least one Cb dicarboxylic acid is C₆-C₁₈Preferably C₆-C₁₂More preferably C₁₀-C₁₂；

When the recurring units A of the copolyamide result from the polycondensation of at least one lactam, the at least one lactam may be chosen from C₉-C₁₈Preferably C₁₀-C₁₈More preferably C₁₀-C₁₂A lactam. C₁₀-C₁₂Lactams are especially decanolactam, undecanolactam and laurolactam.

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

Advantageously, the unit a results from the polycondensation of a single lactam, and the lactam is laurolactam.

When the recurring units A of the copolyamide result from the polycondensation of at least one amino acid, the at least one amino acid may be chosen from C₉-C₁₈Preferably C₁₀-C₁₈More preferably C₁₀-C₁₂An amino acid.

C₉-C₁₂Amino acids are in particular 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.

The units a result from the polycondensation of at least one amino acid and may therefore comprise a single amino acid or a plurality of amino acids.

Advantageously, the unit a results from the polycondensation of a single amino acid, and the amino acid is 11-aminoundecanoic acid.

When the recurring units A of the copolyamide are derived from at least one C₄-C₃₆Preferably C₆-C₁₈Preferably C₆-C₁₂More preferably C₁₀-C₁₂Ca diamine and at least one C₄-C₃₆Preferably C₆-C₁₈Preferably C₆-C₁₂More preferably C₁₀-C₁₂In the polycondensation of Cb diacids, then the at least one Ca-diamine is a linear or branched, in particular linear, aliphatic diamine and the at least one Cb diacid is a linear or branched, in particular linear, aliphatic diacid.

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

The at least one C₄-C₃₆The Ca diamine may in particular be chosen from 1, 4-butanediamine, 1, 5-pentamethylenediamine, 1, 6-hexamethylenediamine, 1, 7-heptamethylenediamine, 1, 8-octamethylenediamine, 1, 9-nonamethylenediamine, 1, 10-decamethylenediamine, 1, 11-undecamethylenediamine, 1, 12-dodecamethylenediamine, 1, 13-tridecamethylenediamine, 1, 14-tetradecamethylenediamine, 1, 16-hexadecamethylenediamine and 1, 18-octadecylenediamine, eicosanediamine, docosane diamine and diamines derived from fatty acids.

Advantageously, the at least one Ca diamine is C₆-C₁₈And is selected from the group consisting of 1, 6-hexamethylenediamine, 1, 7-heptamethylenediamine, 1, 8-octamethylenediamine, 1, 9-nonamethylenediamine, 1, 10-decamethylenediamine, 1, 11-undecamethylene diamine, 1, 12-dodecamethylenediamine, 1, 13-tridecamethylenediamine, 1, 14-tetradecamethylenediamine, 1, 16-hexadecamethylenediamine, and 1, 18-octadecamethylenediamine.

Advantageously, said at least one C₆-C₁₂Ca diamine is selected from 1, 6-hexamethylene diamine, 1, 7-heptamethylene diamine, 1, 8-octamethylene diamine, 1, 9-nonamethylene diamine, 1, 10-decamethylene diamine, 1, 11-undecamethylene diamineDiamines and 1, 12-dodecamethylenediamine.

Advantageously, the Ca diamine used is C₁₀-C₁₂Diamines, in particular from 1, 10-decamethylenediamine, 1, 11-undecamethylene diamine and 1, 12-dodecamethylenediamine.

The at least one C₄-C₃₆The Cb dicarboxylic acid may be selected from succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, octadecenediamine, eicosenediamine, docosanediamine, and diamines derived from fatty acids.

Advantageously, said at least one Cb dicarboxylic acid is C₆-C₁₈And is selected from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid.

Advantageously, said at least one Cb dicarboxylic acid is C₆-C₁₂And may be selected from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid.

Advantageously, said at least one Cb dicarboxylic acid is C₁₀-C₁₂And is selected from sebacic acid, undecanedioic acid, and dodecanedioic acid.

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

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

Said X₁Y units being derived from at least one C₄-C₈Preferably C₄-C₆More preferably C₆Linear aliphatic diamine (X)₁) And at least one aromatic dicarboxylic acid (Y).

The linear aliphatic diamine (X)₁) Selected from among 1, 4-butanediamine, 1, 5-pentamethylenediamine and 1, 6-hexamethylenediamine.

The linear aliphatic diamine (X)₁) Can be the same as or different from the linear aliphatic Ca diamine.

The aromatic dicarboxylic acid (Y) may be C₆-C₁₈、C₆-C₁₈Preferably C₈-C₁₈More preferably C₈-C₁₂。

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

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

The modulus of the composition changes with temperature, and generally the modulus decreases with increasing temperature.

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

Of course, the same applies to other temperature ranges.

The term "wet conditioning" means after saturation in liquid water at 65 ℃.

In other words, for a composition conditioned under the same dry or wet atmosphere conditions, M₂₀M is the modulus measured at 20 deg.C_TFor the modulus measured at temperature T, then:

((M₂₀–M_T)/M₂₀) x 100 is less than or equal to 20, wherein T is 20 to 40 ℃.

Advantageously, for a composition conditioned under the same dry or wet atmosphere conditions, the modulus does not vary by more than 20% in the temperature range from 0 ℃ to 40 ℃, thus ((M)₀–M_T)/M₀) x 100 is less than or equal to 20, wherein T is 0 to 40 ℃.

More advantageously, the modulus does not vary by more than 20% in the temperature range from-10 ℃ to 40 ℃ for compositions conditioned under the same dry or wet atmospheric conditions, thus ((M)_-10–M_T)/M_-10) x 100 is less than or equal to 20, wherein T is-10 to 40 ℃.

Advantageously, for a composition conditioned under the same wet atmosphere conditions, the modulus does not vary by more than 15% in the temperature range from 0 ℃ to 40 ℃, thus ((M)₀–M_T)/M₀) x 100 is less than or equal to 15, wherein T is 0 to 40 ℃.

More advantageously, the modulus does not vary by more than 15% in the temperature range from-10 ℃ to 40 ℃ for compositions conditioned under the same wet atmosphere conditions, thus ((M)_-10–M_T)/M_-10) x 100 is less than or equal to 15, wherein T is-10 to 40 ℃.

Advantageously, for a composition conditioned under the same dry atmosphere conditions, the modulus does not vary by more than 5% in the temperature range from 0 ℃ to 40 ℃, thus ((M)₀–M_T)/M₀) x 100 is less than or equal to 5, wherein T is 0 to 40 ℃.

More advantageously, for compositions conditioned under the same dry atmosphere conditions, the modulus does not vary by more than 5% in the temperature range from-10 ℃ to 40 ℃, thus ((M)_-10–M_T)/M_-10) x 100 is less than or equal to 5, wherein T is-10 to 40 ℃.

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

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

In one embodiment, said X of said copolyamide defined previously₁Y units being through at least one C₄-C₈More preferably C₄-C₆In particular C₆Aliphatic diamine (X)₁) And at least one aromatic dicarboxylic acid (Y).

X₁Examples of Y units are 4I, 4T, 4N, 6I, 6T, 6N.

Advantageously, the copolyamide has the formula A/X₁T。

Advantageously, said X of said copolyamide defined previously₁Y units being through at least one C₄-C₈"Youyou" for curing diabetesLand selection C₄-C₆More preferably C₆Aliphatic diamine (X)₁) Repeating units obtained by polycondensation.

X₁Examples of Y units are 4I, 4T, 4N, 6I, 6T, 6N,

advantageously, X₁Y is selected from 4T and 6T, preferably 6T.

Advantageously, the copolyamide has the formula A/4T or A/6T, preferably A/6T.

In another embodiment, said a unit of said copolyamide defined above is an amino acid or a lactam as defined above.

Advantageously, the copolyamide has the formula A/X₁Y, wherein A is an amino acid or a lactam as defined above and X₁Y is as defined above.

Advantageously, the copolyamide has the formula A/X₁T, wherein a is an amino acid or a lactam as defined hereinbefore.

Advantageously, the copolyamide has the formula A/4T or A/6T, preferably A/6T, where A is an amino acid or a lactam as defined previously.

In another embodiment, said A units of said copolyamide defined previously are each C₁₁Or C₁₂An amino acid or a lactam.

Advantageously, the copolyamide has the formula A/X₁Y, wherein A is C₁₁Or C₁₂Amino acid or lactam and X₁Y is as defined above.

In yet another embodiment, the copolyamide defined above is semicrystalline.

Within the meaning of the present invention, semicrystalline copolyamides are those which are: it has a melting temperature (Tm) by DSC according to ISO standard 11357-3:2013 and an enthalpy of crystallization during a cooling step by DSC at a rate of 20K/min, measured according to ISO standard 11357-3 of 2013, higher than 30J/g, preferably higher than 35J/g.

Thus, in this embodiment, A and X in the copolyamide of the invention are adjusted according to the different units₁Y units, so that the copolyamide is semicrystalline.

In another embodiment, formula A/X₁Said copolyamide of Y consisting only of A and X as defined hereinbefore₁And Y units.

Thus, in this embodiment, the copolyamide has only one or more a units and only one or more X units₁A Y unit; however, a is a repeating unit resulting from the polycondensation of at least one amino acid or at least one lactam or at least one Ca diamine as defined hereinbefore and at least one Cb dicarboxylic acid, and X₁Y is derived from at least one linear aliphatic diamine (X) as defined hereinbefore₁) And at least one aromatic dicarboxylic acid (Y) as defined hereinbefore.

In another embodiment, formula A/X₁Said copolyides of Y consisting of only one A unit and one X unit as defined hereinbefore₁And Y units.

Thus, in this embodiment, the copolyamide has only one or more a units and only one or more X units₁Y units, and A is a repeating unit resulting from the polycondensation of an amino acid or a lactam or at least one Ca diamine as defined hereinbefore and at least one Cb dicarboxylic acid, and X₁Y is derived from a linear aliphatic diamine (X) as defined hereinbefore₁) A recurring unit of polycondensation with an aromatic dicarboxylic acid (Y) as defined hereinbefore.

Advantageously, the copolyamide is chosen from among PA11/4T, PA11/6T, PA12/4T, PA12/6T, PA610/4T, PA610/6T, PA612/4T, PA612/6T, PA1010/4T, PA1012/4T, PA1010/6T, PA1012/6T, PA1210/4T, PA1212/4T, PA1210/6T, PA1212/6T, in particular PA 11/6T.

In another embodiment, the copolyamide comprises at least one of A and X₁A third Z unit different from the Y unit and having the formula A/X₁Y/Z

Wherein:

a and X₁The Y units are as defined above.

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

with the proviso that caprolactam or aminocaproic acid is excluded from the definition of lactam and amino acid of Z, and terephthalic acid is excluded from the definition of Cd diacid when Cc diamine is C10 diamine.

It is clear that when formula A/X₁Said copolyamide of Y consisting only of units A and X as defined previously₁When Y is composed of, or when formula A/X₁Said copolyamide of Y consisting only of one unit A and one unit X as defined above₁When Y constitutes, the third Z unit may not be present.

Nevertheless, in the presence of at least one of A and X₁In this embodiment of a third Z unit different from Y, the copolyamide of the invention may comprise one or more A units and one or more X units₁Y units and at least one Z unit.

The term "different" means that even if there are a plurality of A and/or X₁Y units, Z units, if present, also being present with A and X in the copolyamide₁The Y units are different, but the Z units may however also be of the same type as A, i.e. recurring units derived from the polycondensation of lactams or amino acids, or Ca-diamines with Cb-dicarboxylic acids, or with X₁Y is of the same type, i.e. derived from at least one linear aliphatic C₄-C₈Diamine (X)₁) A repeating unit of polycondensation with at least one aromatic dicarboxylic acid (Y).

When Z represents a unit derived from an amino acid, it may be chosen 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.

When Z represents a unit derived from a lactam, the lactam may be selected from the group consisting of pyrrolidone, 2-piperidone, caprolactam, enantholactam, caprolactam, nonalactam, decanolactam, undecanolactam and laurolactam.

When the Z units are units of the formula (Cc diamine). (Cd diacid), the units (Cc diamine) are selected from aliphatic, linear or branched diamines, alicyclic diamines, and arylaliphatic diamines.

When the diamine is aliphatic and linear, it is selected from butanediamine, pentanediamine, hexanediamine, heptanediamine, octanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, hexadecanediamine, octadecanediamine, octadecenediamine (d ═ 18), eicosanediamine, docosanediamine and diamines derived from fatty acids.

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

When the Cc diamine is cycloaliphatic, it is selected from the group consisting of 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), 1, 3-bis (aminomethyl) cyclohexane (1,3-BAC), 1, 4-bis (aminomethyl) cyclohexane (1,4-BAC) and mixtures thereof. It may also comprise the following carbon skeleton: norbornanemethane, cyclohexylmethane, dicyclohexylpropane, bis (methylcyclohexyl) propane and bis (methylcyclohexyl) propane. A non-exhaustive list of these Cycloaliphatic diamines is given in the publication "Cycloaliphatic Amines" (encyclopedia of Chemical Technology, Kirk-Othmer, fourth edition (1992), page 386-405).

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

The Cd dicarboxylic acids are selected from linear or branched aliphatic diacids, cycloaliphatic diacids and aromatic diacids.

When Cd diacid is aliphatic and linear, it is selected from the group consisting of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, octadecenedioic acid, eicosanedioic acid, docosanedioic acid, and fatty acid dimers containing 36 carbons.

The fatty acid dimers mentioned hereinbefore are dimerised fatty acids obtained by oligomerisation or polymerisation of unsaturated long-chain hydrocarbon monobasic fatty acids (for example linoleic and oleic acids), as described in particular in document EP 0,471,566.

When the diacid is cycloaliphatic, it may comprise the following carbon backbone: norbornanemethane, cyclohexylmethane, dicyclohexylmethane, dicyclohexylpropane, bis (methylcyclohexyl) propane and bis (methylcyclohexyl) propane.

When the diacid is aromatic, it is selected from terephthalic acid (denoted as T), isophthalic acid (denoted as I) and naphthalene dicarboxylic acids (denoted as N).

Excluding caprolactam or aminocaproic acid from the definition of lactam and amino acid of Z, which means that A and X therein₁Y is a group of formula 6/A/X as defined above₁Compounds of Y are excluded.

When Cc diamine is C10 diamine, terephthalic acid is excluded from the definition of Cd diacid, which means where A and X are₁Y is a group of formula 10T/A/X as defined above₁Compounds of Y are excluded.

In one embodiment, the copolyamide is composed of only formula A/X₁Three units of Y/Z.

These three units are as defined above, and the exclusion also applies.

Thus, in this embodiment, there are only three different cells A, X₁Y and Z, but nonetheless one or more A units, one or more X units may be present₁Y units and one or more Z units.

In another embodiment, the copolyamide is composed of only formula A/X₁Y/Z and is in the formula A/X₁Only one A unit and only one X unit exist in Y/Z₁Y units and a Z unit.

In yet another embodiment, the present invention relates to the use of a copolyamide as defined hereinbefore for the preparation of a composition as defined hereinbefore, comprising up to 70% by weight of reinforcing fibres, in particular from 30 to 70% by weight of reinforcing fibres.

According to one embodiment, the composition comprises from 35 to 65% and preferably from 50 to 65% by weight of reinforcing fibres, based on the total weight of the composition.

Throughout the specification, the phrase "… … to … … (between … … and … …)" is intended to be inclusive.

The composition according to the invention may comprise short reinforcing fibres or short reinforcing fibres.

Preferably, the fibres are short and 2-13mm long, preferably 3-8mm long, before the composition is applied.

These short reinforcing fibers may be selected from:

-natural fibres

Mineral fibers, i.e. those fibers having a high melting temperature Tm' higher than the melting temperature Tm of the semi-crystalline copolyamide of the invention and higher than the polymerization and/or implementation temperature.

-polymer fibres having a melting temperature Tm ' or, if no Tm ', a glass transition temperature Tg ' higher than the polymerization temperature or than the melting temperature Tm of the semi-crystalline copolyamide constituting the thermoplastic material matrix and higher than the implementation temperature.

-or mixtures of the above fibres.

Examples of mineral fibers suitable for use in the present invention are: carbon fibers including nanotubes or fibers of Carbon Nanotubes (CNTs), carbon nanofibers or graphene; silica fibers such as glass fibers, particularly E, R, S2 or T-type; boron fibers; ceramic fibers, in particular silicon carbide fibers, boron carbonitride fibers, silicon nitride fibers, boron nitride fibers, basalt fibers or fibers based on basalt; fibers or filaments comprising a metal and/or alloy thereof; metal oxide fibers, in particular aluminum oxide (Al)₂O₃) The fibers of (a); metallized fibers, such as metallized glass fibers and metallized carbon fibers or mixtures of the foregoing.

More particularly, these fibers may be selected as follows:

the mineral fibres may be selected from: carbon fibers, carbon nanotube fibers, glass fibers, in particular of the E, R, S2 or T type, boron fibers, ceramic fibers, in particular silicon carbide fibers, boron carbonitride fibers, silicon nitride fibers, boron nitride fibers, basalt fibers or fibers based on basalt; fibres or filaments containing metals and/or alloys thereof, containing metal oxides, e.g. Al₂O₃Of fibres, of metallized fibres, e.g. metallized glass fibres and metallized carbon fibres, or mixtures of the above, and

-under the above conditions, the polymer fibres are selected from:

-thermosetting polymer fibres, and more particularly selected from: unsaturated polyesters, epoxy resins, vinyl esters, phenolic resins, polyurethanes, cyanoacrylates and polyimides, such as bismaleimide resins, aminoplasts resulting from the reaction of amines, such as melamine, with aldehydes, such as glyoxal or formaldehyde;

-fibres of a thermoplastic polymer, and more particularly selected from: polyethylene terephthalate (PET), polybutylene terephthalate (PBT);

-polyamide fibres;

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

polyamide block copolymers such as polyamide/polyether fibres, Polyaryletherketones (PAEK) such as Polyetheretherketone (PEEK), Polyetherketoneketone (PEKK), Polyetherketoneetherketoneketone (PEKEKK) fibres.

Preferred short reinforcing fibers are short fibers selected from the group consisting of: carbon fibres, including metallised fibres, glass fibres, including metallised fibres such as E, R, S2 or T, aramid fibres (e.g. aramid fibres)) Or aramid, Polyaryletherketone (PAEK) fibers, such as Polyetheretherketone (PEEK), Polyetherketoneketone (PEKK) fibers, Polyetherketoneetherketoneketone (PEKEKK) fibers, or mixtures thereof.

More particularly, the natural fibers are selected from the group consisting of flax fibers, castor fibers, wood fibers, sisal fibers, kenaf fibers, coir fibers, hemp fibers, and jute fibers.

Advantageously, the weight ratio of reinforcing fibres to copolyamide does not exceed 1.75, in particular 1.6.

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

The reinforcing fibers may be:

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

Or have a non-circular cross-section with an L/D ratio (where L represents the maximum dimension of the cross-section of the fiber and D represents the minimum dimension of the cross-section of said fiber) of between 2 and 8, in particular between 2 and 4. L and D can be measured by Scanning Electron Microscopy (SEM).

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

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

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

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

In one embodiment, the composition is free of at least one ingredient selected from the group consisting of: polyphenylene Ether (PPE), anti-drip agents (anti-drip agent), PA46, PA66, PA6, polyamides based on units obtained by polycondensation of caprolactam, free-radical inhibitors, in particular inorganic, flame retardants, nigrosine, elemental iron (elemental iron), polyols, metal oxides selected from magnesium oxide, zinc oxide, calcium oxide or mixtures thereof, amino acid heat stabilizers having at least one hydroxyl group and amorphous polyamides.

In one embodiment, if the composition comprises titanium oxide, it is free of metal oxides selected from magnesium oxide, zinc oxide, calcium oxide, or mixtures thereof.

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

-0-10% by weight of at least one impact modifier;

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

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

from 0 to less than 2%, preferably from 0.5 to less than 2%, by weight of additives,

wherein the sum of copolyamide, reinforcing fiber, impact modifier, filler, fluidizing agent and additive equals 100%.

In the latter embodiment, advantageously, the composition is free of at least one excluded ingredient as defined hereinbefore.

In one embodiment, the invention thus relates to formula A/X as defined hereinbefore₁Y comprising at least two different units A and X₁Use of a copolyamide of Y to prepare a composition comprising:

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

-from 30 to 70% by weight of reinforcing fibres,

-0-10% by weight of at least one impact modifier;

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

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

from 0 to less than 2%, preferably from 0.5 to less than 2%, by weight of additives,

wherein the sum of copolyamide, reinforcing fiber, impact modifier, filler, fluidizing agent and additive equals 100%.

And the modulus of the composition does not vary by more than 20% in the temperature range of 20 ℃ to 40 ℃, in particular in the temperature range of 0 ℃ to 40 ℃, in particular in the temperature range of-10 ℃ to 40 ℃, as defined hereinbefore.

In another embodiment, the invention thus relates to formula A/X as defined hereinbefore₁Y comprising at least two different units A and X₁Use of a copolyamide of Y to prepare a composition comprising:

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

35-65% and preferably 50-65% by weight of reinforcing fibres,

-0-10% by weight of at least one impact modifier;

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

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

from 0 to less than 2%, preferably from 0.5 to less than 2%, by weight of additives,

wherein the sum of copolyamide, reinforcing fiber, impact modifier, filler, fluidizing agent and additive is 100% and the modulus of the composition does not change more than 20% in the temperature range of 20 ℃ to 40 ℃, in particular in the temperature range of 0 ℃ to 40 ℃, especially in the temperature range of-10 ℃ to 40 ℃, as defined hereinbefore.

Advantageously, the invention thus relates to the formula A/X as defined hereinbefore₁Y comprising at least two different units A and X₁Use of a copolyamide of Y to prepare a composition comprising:

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

35-65% and preferably 50-65% by weight of reinforcing fibres,

-0-10% by weight of at least one impact modifier;

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

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

from 0 to less than 2%, preferably from 0.5 to less than 2%, by weight of additives,

wherein the sum of copolyamide, reinforcing fiber, impact modifier, filler, fluidizing agent and additive is 100% and the modulus of the composition does not change more than 20% in the temperature range of 20 ℃ to 40 ℃, in particular in the temperature range of 0 ℃ to 40 ℃, especially in the temperature range of-10 ℃ to 40 ℃, as defined hereinbefore.

More advantageously, the invention thus relates to formula A/X as defined hereinbefore₁Y comprising at least two different units A and X₁Use of a copolyamide of Y to prepare a composition comprising:

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

35-65% and preferably 50-65% by weight of reinforcing fibres, in particular 50-62% by weight of reinforcing fibres,

-0-10% by weight of at least one impact modifier;

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

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

from 0 to less than 2%, preferably from 0.5 to less than 2%, by weight of additives,

wherein the sum of copolyamide, reinforcing fiber, impact modifier, filler, fluidizing agent and additive is 100% and the modulus of the composition does not change more than 20% in the temperature range of 20 ℃ to 40 ℃, in particular in the temperature range of 0 ℃ to 40 ℃, especially in the temperature range of-10 ℃ to 40 ℃, as defined hereinbefore.

In yet another embodiment, the composition consists of a copolyamide, reinforcing fibers, and the following:

-0-10% by weight of at least one impact modifier;

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

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

from 0 to less than 2%, preferably from 0.5 to less than 2%, by weight of additives,

wherein the sum of copolyamide, reinforcing fiber, impact modifier, filler, fluidizing agent and additive equals 100%.

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

Advantageously, in this further embodiment, the invention thus relates to formula a/X as defined hereinbefore₁Y comprising at least two different units A and X₁Use of a copolyamide of Y for the preparation of a composition consisting of:

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

-from 30 to 70% by weight of reinforcing fibres,

-0-10% by weight of at least one impact modifier;

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

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

from 0 to less than 2%, preferably from 0.5 to less than 2%, by weight of additives,

wherein the sum of copolyamide, reinforcing fiber, impact modifier, filler, fluidizing agent and additive is 100% and the modulus of the composition does not change more than 20% in the temperature range of 20 ℃ to 40 ℃, in particular in the temperature range of 0 ℃ to 40 ℃, especially in the temperature range of-10 ℃ to 40 ℃, as defined hereinbefore.

Advantageously, in this further embodiment, the invention thus relates to formula a/X as defined hereinbefore₁Y comprising at least two different units A and X₁Use of copolyamides of Y for preparing compositions, and use of copolyamides of Y for preparing compositionsThe composition consists of the following components:

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

35-65% and preferably 50-65% by weight of reinforcing fibres,

-0-10% by weight of at least one impact modifier;

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

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

from 0 to less than 2%, preferably from 0.5 to less than 2%, by weight of additives,

wherein the sum of copolyamide, reinforcing fiber, impact modifier, filler, fluidizing agent and additive is 100% and the modulus of the composition does not change more than 20% in the temperature range of 20 ℃ to 40 ℃, in particular in the temperature range of 0 ℃ to 40 ℃, especially in the temperature range of-10 ℃ to 40 ℃, as defined hereinbefore.

Advantageously, the invention thus relates to the formula A/X as defined hereinbefore₁Y comprising at least two different units A and X₁Use of a copolyamide of Y for the preparation of a composition consisting of:

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

35-65% and preferably 50-65% by weight of reinforcing fibres, in particular 50-62% by weight of reinforcing fibres,

-0-10% by weight of at least one impact modifier;

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

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

from 0 to less than 2%, preferably from 0.5 to less than 2%, by weight of additives,

wherein the sum of copolyamide, reinforcing fiber, impact modifier, filler, fluidizing agent and additive is 100% and the modulus of the composition does not change more than 20% in the temperature range of 20 ℃ to 40 ℃, in particular in the temperature range of 0 ℃ to 40 ℃, especially in the temperature range of-10 ℃ to 40 ℃, as defined hereinbefore.

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

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

The composition may further comprise one or more impact modifiers as defined hereinbefore. The presence of the impact modifier allows greater extensibility to be imparted to the article being manufactured.

The polyolefin of the impact modifier may be functionalized or unfunctionalized, or may comprise both in admixture.

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

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

Advantageously, the impact modifier is selected from:F493，in particular40R53 SP01， VA1803 or VA1801, and,IM800, or mixtures of these, in this case in a ratio in the range from 0.1/99.9 to 99.9/0.1.

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

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

According to certain embodiments, the impact modifier may be present in an amount of 0 to 10% by weight, advantageously 1 to 10% by weight, relative to the total weight of the composition.

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

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

About the filler

The composition may also comprise a filler. Fillers contemplated include conventional mineral fillers such as kaolin, magnesite, slag, carbon black, expanded or unexpanded graphite, wollastonite, nucleating agents such as silica, alumina, clay or talc, especially talc, pigments such as titanium oxide and zinc sulfide, and antistatic fillers.

The composition may also comprise a fluidizing agent.

The term "fluidizing agent" especially includes prepolymers.

The prepolymer may be selected from linear or branched aliphatic, cycloaliphatic, semi-aromatic or aromatic polyamide oligomers. The prepolymer may also be a copolyamide oligomer or a mixture of a polyamide and a copolyamide oligomer. Preferably, the prepolymer has a number average molecular weight Mn of 1000-. In particular, if the chain limiter (chain limiter) used is, for example, a monoamine, the prepolymer may be a monofunctional NH₂. The number average molecular weight (Mn) or the amine number is calculated according to the following formula: mn 1000/[ NH ]₂]In which [ NH ]₂]Is the concentration of amine functional groups in the copolyamide as determined, for example, by potentiometric titration.

According to certain embodiments, the content of fluidizing agent may be from 0 to 5% by weight, in particular from 1 to 5% by weight, relative to the total weight of the composition.

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

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

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

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

The stabilizer may be an organic or mineral stabilizer. Typical stabilizers for use with polymers include phenols, phosphites, UV absorbers, HALS (hindered amine light)Stabilizer) stabilizer and metal iodide. Examples include from BASF1010. 245, 1098 from BASF168. 126 from BASF312. 770, Iodide P201 from Ciba, and ClariantS-EED。

The lubricant may contain a stearate or wax binder.

The wax may in particular be an amorphous wax, such as beeswax, silicone wax (silicone wax), polyethylene wax, oxidised polyethylene wax, ethylene copolymers, montan wax (montan wax) and polyether waxes.

A plurality of different additives of the same or different classes may be present in the composition.

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

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

According to some embodiments, the additive may be present in the composition in an amount of 0 to 0.5% by weight; or 0.1 to 0.5% by weight; or 0.5 to 1% by weight; or 1-1.5% by weight; or 1.5 to less than 2% by weight.

According to a second aspect, the present invention relates to a composition, in particular for injection moulding, comprising:

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

-30-65, in particular 50-65, and more in particular 50-62% by weight of reinforcing fibres;

-0-10% by weight of at least one impact modifier;

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

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

from 0 to less than 2%, preferably from 0.1 to less than 2%, in particular from 0.5 to less than 2%, by weight of additives,

provided that the reinforcing fibers are non-circular in cross-section and have a cross-section of 1.5 to 5.0X 10^-6cm²The weight ratio of reinforcing fibres to copolyamide does not exceed 1.75, in particular 1.6;

the sum of the proportions of the ingredients of the composition is equal to 100%.

Thus, the pairs have a length of 1.5-5.0X 10^-6cm²The exclusion of the non-circular cross-section reinforcing fibers of cross-sectional area of (a) is valid for both the ratio of 1.75 and the ratio of 1.6.

In one embodiment, the composition particularly useful for injection molding comprises:

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

-30-65, in particular 50-65, and more in particular 50-62% by weight of reinforcing fibres;

-0-10% by weight of at least one impact modifier;

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

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

from 0 to less than 2%, preferably from 0.1 to less than 2%, in particular from 0.5 to less than 2%, by weight of additives,

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

the sum of the proportions of the ingredients of the composition is equal to 100%.

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

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

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

-30-65, in particular 50-65, and more in particular 50-62% by weight of reinforcing fibres;

-0-10% by weight of at least one impact modifier;

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

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

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

the sum of the proportions of the ingredients of the composition is equal to 100%.

The reinforcing fibers, impact modifiers, fluidizers, fillers, and additives are as previously defined, and all concentration ranges as previously defined with respect to impact modifiers, fillers, fluidizers, and additives are also effective for the composition itself.

The exclusion defined above is also valid for the preparation of the composition.

Advantageously, the composition particularly useful for injection molding consists of:

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

-30-65, in particular 50-65, and more in particular 50-62% by weight of reinforcing fibres;

-0-10% by weight of at least one impact modifier;

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

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

from 0 to less than 2%, preferably from 0.1 to less than 2%, in particular from 0.5 to less than 2%, by weight of additives,

provided thatIf the cross-section of the reinforcing fibres is non-circular and has a size of 1.5-5.0X 10^-6cm²The weight ratio of reinforcing fibres to copolyamide does not exceed 1.75, in particular 1.6;

the sum of the proportions of the ingredients of the composition is equal to 100%.

Thus, the pairs have a length of 1.5-5.0X 10^-6cm²The exclusion of the non-circular cross-section reinforcing fibers of cross-sectional area of (a) is valid for both the ratio of 1.75 and the ratio of 1.6.

In one embodiment, the composition particularly useful for injection molding consists of:

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

-30-65, in particular 50-65, and more in particular 50-62% by weight of reinforcing fibres;

-0-10% by weight of at least one impact modifier;

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

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

from 0 to less than 2%, preferably from 0.1 to less than 2%, in particular from 0.5 to less than 2%, by weight of additives,

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

the sum of the proportions of the ingredients of the composition is equal to 100%.

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

In another embodiment, the composition particularly useful for injection molding consists of:

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

-30-65, in particular 50-65, and more in particular 50-62% by weight of reinforcing fibres;

-0-10% by weight of at least one impact modifier;

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

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

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

the sum of the proportions of the ingredients of the composition is equal to 100%.

Advantageously, said copolyamide of said composition is selected from PA11/4T, PA11/6T, PA12/4T, PA12/6T, PA1010/4T, PA1012/4T, PA1010/6T, PA1012/6T, in particular PA 11/6T.

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

Advantageously, the glass fibers of the composition are chosen from glass fibers of non-circular cross section and of circular cross section, carbon fibers and mixtures thereof, in particular glass fibers of non-circular cross section and of circular cross section and mixtures thereof, in particular glass fibers of non-circular cross section.

The glass fibers are as defined above.

According to a third aspect, the present invention relates to a process for manufacturing a composition as defined hereinbefore, wherein the ingredients of the composition are mixed by compounding, in particular in a twin-screw extruder, preferably a co-rotating extruder, blender or internal mixer (internal mixer).

Finally according to a fourth aspect, the invention relates to a moulded article obtainable by injection moulding from a composition as defined hereinbefore.

Advantageously, the molded article is used in electrical applications and electronic equipment, and is in particular selected from television sets, digital cameras, digital game machines, telephone parts, digital tablets, drones, printers or computer parts.

Examples

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

Example 1: synthesis of the copolyamide of the invention.

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

Synthesis of CoPa 11/6T representatives of various copolyamides:

aminoundecanoic acid, hexamethylenediamine and terephthalic acid monomers are charged together in the reactor according to the desired mass ratio. The medium is first inerted to remove oxygen that may cause yellowing or side reactions. Water may also be added to improve heat exchange. A plateau with two temperature and pressure increases (Deux paliers de mont et temp. set pressure solvent realis) was carried out. The temperature (T °) and pressure conditions are chosen to allow the medium to melt. After the maintenance conditions are reached, degassing is carried out to allow the polycondensation reaction to proceed. The medium gradually became viscous and nitrogen purge or application of vacuum resulted in the formation of water of reaction. When a stop condition associated with the desired viscosity is reached, stirring is stopped and extrusion and granulation can begin. The particles obtained are subsequently compounded with glass fibers.

Compounding

The composition is prepared by mixing the polymer particles while in the melt. The mixture was made by compounding on a twin screw co-rotating MC26 extruder with a flat temperature profile (T °) at 290 ℃. The screw speed was 250rpm and the flow rate was 20 kg/h.

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

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

The following compositions were prepared (E ═ inventive example CE ═ comparative example):

[ Table 1]

245 and168 is an antioxidant

Circular cross-section fiber CSX 451J and non-circular cross-section fiber CSG 3PA820 (also known as flat fiber) are sold by Nittobo corporation.

Injection of drugs

Preparation of 100 x 1mm by injection of different compositions³The plate material of (2):

-injection temperature: 300 deg.C

-moulding temperature: 80 deg.C

The cycle time is adjusted according to the composition to allow injection of the composition and is less than 50 seconds.

Example 2: change in flexural modulus after Water absorption

To evaluate the effect of moisture on flexural modulus, the flexural modulus of a sample of the obtained composition was measured on an Instron 5966 machine manufactured by the Instron company. The compositions are dry compositions and compositions previously saturated in water at 65 ℃.

The tests were carried out at different temperatures from-10 ℃ to 60 ℃.

In the injection-molded panels, test specimens having dimensions according to ISO 178 but a thickness of 1mm were cut out in the injection direction.

The results are shown in table 2 and the tables thereafter:

[ Table 2]

[ Table 3]

[ Table 4]

[ Table 5]

[ Table 6]

Example 3: change in tensile modulus after Water absorption

To evaluate the effect of moisture on tensile modulus, the tensile modulus of samples of the obtained composition was measured on an Instron 5966 machine manufactured by the Instron company, the composition being a dry composition and a composition previously saturated in water at 65 ℃.

The tests were carried out at different temperatures from-10 ℃ to 60 ℃.

In the injection-molded panels, test specimens having dimensions according to ISO 527 but a thickness of 1mm were cut out in the injection direction.

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

Tables 2-4 and example 3 show that the compositions of the present invention have higher modulus stability for both flexing and stretching than the comparative compositions CE1 and CE 2.