EP2622019A1

EP2622019A1 - Peba composition and use thereof for manufacturing a transparent object resistant to high-speed impacts

Info

Publication number: EP2622019A1
Application number: EP11773789.0A
Authority: EP
Inventors: Sophie Chhun; Benjamin Saillard; Frédéric MALET; Jérôme ALLANIC
Original assignee: Arkema France SA
Current assignee: Arkema France SA
Priority date: 2010-09-28
Filing date: 2011-09-27
Publication date: 2013-08-07
Also published as: FR2965269B1; US20130202831A1; TW201231514A; JP2013538912A; KR20130115224A; CN103124770A; FR2965269A1; WO2012042162A1

Abstract

The present invention relates to the use of a copolymer comprising polyether (PE) blocks and polyamide (PA) blocks for manufacturing a transparent object that is resistant to high-speed impacts and resistant to shocks, wherein said copolymer has the following characteristics: said PA blocks include more than 50 mol % of an equimolar combination of at least one cycloaliphatic diamine and at least one aliphatic carboxylic diacid having 12 to 36 carbon atoms; said PA blocks constitute 20 to 90 wt % of the total weight of the copolymer; the numerical molecular weight of the PA blocks is within the range of 1,000 to 10,000 g/mol; said PE blocks constitute 10 to 80 wt % of the total weight of the copolymer; and the numerical molecular weight of the PE blocks is between 200 and 1,000 g/mol.

Description

PEBA-based composition and its use for the manufacture of a transparent object resistant to high speed impact Description

The invention relates to the use of novel compositions of thermoplastic polymers used in the manufacture of objects which combine excellent properties of transparency and high-speed impact resistance. The invention more particularly relates to the manufacture of transparent protective equipment, such as safety glasses, ballistic windows, armored windows, helmets, visors, etc.

Of the transparent polymers, polycarbonate (PC) is used in situations where protection is the main criterion. Polycarbonate is characterized by its resistance to impact, but its transparency is less compared to glass. The first windows and bulletproof windows were made of polycarbonate.

There is also impact-reinforced polyamide (PA), for example the impact-reinforced polyamide BACM.12, that is to say reinforced by a shock modifier or shock reinforcement, such as a modified polyolefin. The materials formed from these PAs have the advantage of being light, but their transparency, their high-speed impact resistance, and their impact resistance are lower than that of the PC.

In addition, the high glass transition temperature (Tg), higher than 150 ° C, of the PC and these transparent PA reinforced shock, can make the transformation (including the injection) of these materials more difficult, with sometimes problems of withdrawal of material.

Today we are looking for an alternative to the PC with materials that are more transparent, more resistant to high-speed impact and impact, lighter, more flexible, with better chemical resistance than the PC, and easy to implement with processes or devices for shaping existing polymers.

More specifically, the present invention aims to provide novel polymer compositions for the manufacture of an object made of material: - "transparency" such that the transmittance of the material is at least 90% at 560 nm on a 2 mm thick plate (according to ISO 13468),

- 'high-speed impact resistant', that is to say a velocity impact of at least 76,2 m / s (250 ft / s) according to EN 166, preferably at least 198 m / s (ie 650 feet / second or 650 ft / s),

- Charpy "impact resistance" notched at least 90 kJ / m according to ISO 179 leU,

- "light" of density less than 1.05 g / cm ³ measured according to ISO 1183 D,

- "chemical resistance" or "solvent resistance" such that the material is capable of deforming by at least 3% without breaking, in flexing immersion in a solvent, such as isopropanol (stress cracking according to the standard ISO 22088-3),

"Flexible": having an elastic modulus of less than 1000 MPa, preferably less than 800 MPa, measured according to ISO 527-2: 93-1BA.

The present invention also aims to provide a method of manufacturing such objects that is simple, easy to implement, fast (which has the least possible steps), and avoids the problems of withdrawal, especially after injection.

We have now found a way to obtain an object combining all these properties by the use of a particular range of polyamide block copolymers and polyether blocks according to the invention, alone or in admixture with at least one transparent amorphous polyamide.

The "polyether block copolymers and polyamide blocks" are hereinafter abbreviated "PEBA".

The copolymers suitable for use according to the invention correspond to a particular range of PEBA selected in the family of amorphous PEBA (delta Hm (2)) = 0 J / g) or which have a crystallinity such as the enthalpy of fusion ( delta Hm (2)) during the second heating of an ISO DSC is at most equal to 30 J / g, the mass being based on the amount of amide units contained or polyamide content, this fusion corresponding to that of amide units . This family of amorphous or very little semi-crystalline PEBAs, and their method of obtaining are described in patent application WO2008006987 of page 5 line 19 to page 9 line 35.

Detailed description of the invention

In the present description, it is specified that:

- the boundaries are excluded when writing "between" two terminals, and

- the terminals are included when writing "the range of X to Z" or "represent 20 to 90%".

The present invention therefore relates to the use of a polyether block copolymer and polyamide blocks for the manufacture of an object:

- transmittance transparency of at least 90% at 560 nm on a 2 mm thick plate (according to ISO 13468).

- resistant to a high speed impact of at least 76.2 m / s (250 ft / s) according to EN 166, and

- Charpy impact resistance notched at least 90 U / m ² according to ISO 179 leU,

and preferably also:

- chemical resistance such that it is capable of deforming in bending immersion in a solvent according to ISO 22088-3 of at least 3% without breaking,

- Light density of less than 1.05 g / cm ³ measured according to ISO 1183 D, flexible have an elastic modulus of less than 1000 MPa, preferably less than 800 MPa, measured according to ISO 527-2: 93- 1BA,

wherein said copolymer has the following characteristics.

For the purposes of the invention, the expression "block copolymer (s) PE and block (s) PA" covers in particular PEBA comprising one or more PE blocks and one or more PA blocks.

According to the present invention, said PA blocks comprise more than 50 mol% of an equimolar association of at least one cycloaliphatic diamine and at least one aliphatic dicarboxylic acid, preferably predominantly (to more than 50 mol%) linear, having from 12 to 36, preferably from 12 to 18, carbon atoms. This particular composition of PA blocks (content and chemistry) of the PEBA contributes in particular to obtaining a compliant transparency (transmittance at least equal to 90%) to the requirements of the invention.

According to a preferred embodiment, the PA blocks of the copolymer used in the invention comprise more than 70%, preferably more than 80%, preferably more than 90%, preferably 100%, in moles, of an equimolar association. at least one cycloaliphatic diamine and at least one aliphatic dicarboxylic acid, preferably linear, having from 12 to 18 carbon atoms.

Said at least one cycloaliphatic diamine is advantageously chosen 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 (abbreviated as "B ACM" or "MACM" or " B "), p-bis (aminocyclohexyl) methane (PACM), isopropylidenedi (cyclohexylamine) (PACP), isophoronediamine (IPD), 2,6-bis (amino methyl) norbornane (BAMN), and mixtures thereof .

Advantageously, a single cycloaliphatic diamine, in particular bis (3-methyl-4-aminocyclohexyl) -methane, is used as a diamine for obtaining PA blocks.

At least one non-cycloaliphatic diamine may enter into the composition of the monomers of the PA blocks, in a proportion of at most 30 mol% (in moles) relative to the diamines of said composition. Non-cycloaliphatic diamines that may be mentioned are linear aliphatic diamines, such as 1,4-tetramethylene diamine, 1,6-hexamethylenediamine, 1,9-nonadiamine and 1,10-decamethylenediamine.

The C 2 -C 18 aliphatic carboxylic acid diacid is preferably selected from 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid and 1,18-octadecanedicarboxylic acid.

The dicarboxylic acid may optionally be at least partially branched by at least one C 1 to C 3 alkyl group (having 1 to 3 carbon atoms).

At least one non-aliphatic dicarboxylic acid can be used in the composition of the monomers of the PA blocks at a rate of at most 15 mol% relative to the dicarboxylic acids of the PAs. Preferably, the dicarboxylic acid non-aliphatic is chosen from aromatic diacids, in particular isophthalic acid (I), terephthalic acid (T) and mixtures thereof.

The term "monomer" in the present description of polyamides should be understood as "repetitive unit". Indeed, the case where a repeating unit of the PA consists of the combination of a diacid with a diamine is particular. It is considered that it is the combination of a diamine and a diacid, that is to say the diamine.diacide couple (in equimolar quantity), which corresponds to the monomer. This is explained by the fact that, individually, the diacid or the diamine is only a structural unit, which is not enough on its own to polymerize.

Said PA blocks may optionally comprise less than 50 mol% of at least one polyamide comonomer, that is to say a monomer of different composition from said equimolar majority association defined above.

Thus, the comonomer comprises, for example, a linear C10 (10 carbon atoms) carboxylic diacid.

Preferably, said PA block comprises less than 30 mol%, preferably less than 20%, preferably less than 10% of polyamide comonomer (s), said at least one comonomer may be chosen from lactams, alpha-acids and omega aminocarboxylic acids, diamine.diacid combinations different from that defined above, and mixtures thereof.

The lactam is, for example, selected from caprolactam, oenantholactam and lauryl lactam. The alpha-omega-aminocarboxylic acid is, for example, selected from aminocaproic acid, 7-amino-heptanoic acid, 11-amino-undecanoic acid or 12-amino-dodecanoic acid.

Preferably, the PA blocks are formed essentially (at more than 80 mol%) from at least one monomer selected from B.12, B.14, B.16, B.18, their copolymers (copolyamides) and / or blocks, and mixtures thereof.

Said PA blocks represent 20 to 90% by weight, preferably 40 to 80% by weight, preferably 60 to 80% by weight, relative to the total weight of the copolymer used according to the invention.

The number-average molecular weight of the PA blocks is in the range from 1000 to 10000 g / mol, preferably from 1500 to 7000 g / mol. The low masses give a copolymer of low glass transition temperature Tg from 75 at 80 ° C, while the highest molecular weights set the Tg of the copolymer at around 150 ° C.

The Tg of the block copolymers used according to the invention is therefore advantageously in the range of 75 ° C. to 150 ° C., preferably in the range of 90 ° C. to 150 ° C. Advantageously, the injection molding of the copolymers and compositions according to the invention is possible at a lower temperature than that required for PC injection, in particular at a temperature below 150 ° C., or even below 100 ° C. The injection of PEBA or the composition comprising it according to the invention is easy, and causes very little shrinkage after injection, which makes it possible to obtain parts of high dimensional accuracy.

In addition, conventional methods of coating type "hard-coating" rather today made at temperatures near the upper limit of Tg (150 ° C) are also possible on the flexible and transparent objects obtained according to the invention.

The PE block components are 10 to 80% by weight, preferably 20 to 60% by weight, preferably 20 to 40% by weight, based on the total weight of the copolymer. Indeed, the PE block content is at least 10% to ensure impact strength and high speed impact resistance sufficient for the uses of the invention.

The number-average molecular mass of the PE blocks is between 200 and 1000 g / mol (excluding bounds), preferably in the range of 400 to 800 g / mol (inclusive), preferably 500 to 700 g / mol.

It turns out that the molecular weight of the PE blocks must be less than 1000 g / mol to guarantee a transparency such that the transmittance of an object according to the invention is at least equal to 90%.

The PE blocks (polyether) are for example derived from at least one polyalkylene ether polyol, in particular a polyalkylene ether diol, preferably chosen from polyethylene glycol (PEG), polypropylene glycol (PPG) and polytrimethylene glycol (PO 3 G). polytetramethylene glycol (PTMG) and mixtures or copolymers thereof. The PE blocks can comprise polyoxyalkylene sequences with NH 2 chain ends, such sequences being obtainable by cyanoacetylation of polyoxyalkylene alpha-omega dihydroxylated sequences. aliphatics called polyetherdiols. More particularly, it is possible to use Jeffamines (for example Jeffamine® D400, D2000, ED 2003, XTJ 542, commercial products from Huntsman).

Said at least one PE block preferably comprises at least one polyether chosen from polyalkylene ether polyols, such as PEG, PPG, PO 3 G, PTMG, polyethers containing polyoxyalkylene sequences with NH 2 chain ends, and their copolymers (copolyethers). ) statistics and / or blocks, and their mixtures,

The present invention also relates to the use of a thermoplastic polymeric composition containing:

from 30 to 99.99%, preferably from 40 to 99.99% by weight of copolymer according to the invention as defined above,

from 0.01 to 70%, preferably from 0.01 to 60% by weight of at least one at least partially transparent, at least partially cycloaliphatic, amorphous polyamide, preferably non-aromatic,

from 0 to 20% of additives,

on the total weight of the composition,

for the manufacture of an object of transparency, high-speed impact resistance, impact resistance, and even chemical resistance, density, and flexibility in accordance with those defined above according to the invention.

"Transparent amorphous polyamides" means amorphous transparent polyamides (delta Hm (2)) = 0 J / g) or very little semi-crystalline (melting enthalpy during the second DSC heating of less than 30 J / g), rigid (ISO bending modulus> 1300 MPa), not deforming under heat, at 60 ° C, because of glass transition temperature Tg greater than 75 ° C. However, they are not very resistant to shock, having a much lower ISO Charpy impact notched compared to the impact modified polyamides, and their chemical resistance is not excellent especially because of their amorphous nature. There are also - but these are less common materials - semi-crystalline (or micro-crystalline) transparent polyamides, typically with melting enthalpies during the second DSC heating between 2 and 30 J / g, these materials being also quite rigid, having an ISO flexural modulus> 1000 MPa. Transparent amorphous polyamides (homopolyamides or copolyamides) that can be used in the compositions according to the invention are described in particular in patent documents EPI 595907 and WO09153534. By way of example of transparent amorphous polyamides, mention may be made of PA B.12, PA 11 / B.14 and PA 11 / B.10.

Preferably, the transparent amorphous PAs used according to the invention are non-aromatic, so as not to increase the Tg of the composition, to facilitate the homogenization of the composition, not to increase the temperature of transformation or shaping of the composition. composition, and not to risk degrading the PEBA (s) of the composition.

The chemical composition of said amorphous polyamide is preferably chosen from the compositions already described for the polyamide blocks of the PEBAs above, which ensures compatibility of the PA with the PEBA.

The addition, from 30%, preferably from 40% by weight, of a block copolymer according to the invention to an amorphous transparent polyamide according to the composition of the invention makes it possible to render said transparent polyamide resistant to High speed impact and shock resistant while keeping its transparency properties.

Said copolymer and the amorphous PA used in the composition of the invention preferably have substantially the same refractive index measured according to ISO 489. It is also possible to modify the nature of the raw materials used to synthesize PEBA and PA. . In general, the addition of an aromatic compound (for example an aromatic diacid) increases the refractive index of a product. For the PEBAs according to the invention, the refractive index decreases if, for example, the PTMG content is increased, relative to the pure PA of the same composition as the PA block of the PEBA. In the BMACM.Y series of PAs, Y being an aliphatic diacid, the longer Y is, the lower the refractive index. For a linear aliphatic PA, the more the number of CH2 increases in the pattern, the lower the refractive index.

If there is an additive in the composition, it is present from 0.01 to 20%, preferably from 0.01 to 10%, preferably from 0.01 to 5%, by weight relative to the total weight of the composition. composition. The additive is chosen in particular from coloring agents, in particular pigments, dyes and effect pigments, such as pigments. diffractants, interferential pigments, such as nacres, reflective pigments and mixtures thereof; anti-UV agents, anti-aging agents, antioxidants, fluidizing agents, anti-abrasion agents, release agents, stabilizers, plasticizers, impact modifiers, surfactants, brighteners, fillers, fibers, waxes and mixtures thereof, and / or any other additive well known in the field of polymers.

Among the fillers, there may be mentioned silica, carbon black, carbon nanotubes, expanded graphite, titanium oxide or glass beads.

The use according to the invention makes it possible to obtain a more transparent object which is more resistant to high-speed impact, more resistant to impact, preferably also more resistant to chemical solvents, lighter, more flexible and easier to handle. to implement an object of the same form in PC, as shown in Table 1 of the examples below.

The subject of the present invention is also a transparent thermoplastic polymer composition based on polyamide, said composition comprising:

from 30 to 100%, preferably from 40 to 100% by weight of copolymer according to the invention as defined above,

from 0 to 70%, preferably from 0 to 60% by weight, of at least one at least partially transparent cycloaliphatic transparent amorphous polyamide, preferably non-aromatic, and more preferably of the same refractive index measured according to the ISO 489 standard that said copolymer, and as described above,

from 0 to 20% of additive,

on the total weight of the composition.

If there is an additive, it is present from 0.01 to 20%, preferably from 0.01 to 10%, preferably from 0.01 to 5%, by weight relative to the total weight of the composition. The additive is chosen in particular from those already described above.

According to one embodiment, the composition of the invention is manufactured by compounding or by dry blending ("dry blend") of its various components. Dry mixing is preferred because it comprises fewer steps and generally results in less pollution (black spots, gels) of the composition than by compounding. Said composition can be used according to the invention to manufacture granules or powders, which can be in turn used in conventional polymer shaping processes for the manufacture of filaments, tubes, films, plates and / or or molded objects that are transparent and resistant to high-speed impact.

The subject of the present invention is in particular a method for manufacturing a transparent object that is resistant to high-speed impact, said method comprising:

- A copolymer supply step according to that defined above;

an optional step of mixing said copolymer with at least one transparent amorphous PA and / or at least one additive, so as to manufacture a composition as defined above;

a stage of implementation, in particular in a mold or a die, of the copolymer or of the composition at a temperature T 0 in the range of 80 to 180 ° C, preferably 90 to 150 ° C;

- then a step of recovery of the transparent object.

By "implementation" is meant here any process of shaping polymers, such as molding, injection, extrusion, coextrusion, hot pressing, multi-injection, rotational molding, sintering, laser sintering, etc., from the composition or copolymer according to the invention.

For the process of manufacturing objects, in particular molded, injected or extruded according to the invention, the granules are preferred. It is more rarely used powders of median diameter by volume (measured according to ISO 9276 - parts 1 to 6) in the range of 400 to 600 μιη. According to a particular mode of shaping of the process of the invention, in particular by sintering such as "laser sintering" or by rotomoulding, the compositions according to the invention are preferably in the form of powder whose particles have a diameter median volume less than 400 μιη, preferably less than 200 μηι. Powder manufacturing methods include cryogenic milling and microganulation.

Another possible embodiment of the method of the present invention may further comprise a preliminary step of compounding PEBA with dyes, and / or any other additive, before said step of manufacturing granules or powder.

The invention also relates to the use of a PEBA and / or a thermoplastic composition as defined above for the manufacture of transparent protective equipment, industrial safety equipment, such as glasses, frames and / or safety glasses, a ballistic glass, a transparent anti-shock plate, a helmet, a visor, a shield, a diving suit; sports equipment; a watch glass; space equipment, including satellite, space shuttle; aeronautical or automotive equipment, such as a windshield, a window, a porthole, a cockpit, an airplane canopy, a window, a bullet-proof glass, in particular a car or a construction window, a glass pane, projector, lighthouse; a display window, in particular advertising, electronic, computer; a screen element; a panel of thermal, solar, photovoltaic panel; an article in the building, furnishing, appliance and decoration industry; play, toy; fashion, such as shoe heels, jewelry; furniture, such as a table, seat, armchair; an article or presentation element; packaging, case, case; container, flask, perfume article, cosmetic or pharmaceutical industry; a bag ; a protection element during transport.

The present invention also relates to any transparent object and resistant to a high-speed impact, of composition as defined above. Preferably, the object according to the invention has these advantageous properties even if it has a small thickness in the range of 0.1 to 10 mm, preferably 0.1 to 3 mm, preferably 0, 5 to 2 mm.

Examples

The examples below illustrate the present invention without limiting its scope. In the examples, unless otherwise indicated, all percentages and parts are by weight.

Several types of transparent PEBA are tested alone or in admixture with a transparent amorphous polyamide and compared to polycarbonate (PC) and B.12 polyamide reinforced with a modified polyolefin.

- Transparent amorphous polyamides used: PA B.12 represents the monomeric polyamide formed by the diamine pair BMAC and dodecanedioic acid (Grilamid TR 90, marketed by EMS). PA 11 / B.14 is a copolyamide comprising 94 mol% of a monomer B.14 (in which "14" represents tetradecanedioic acid) and 6 mol% of a comonomer formed by amino-11-undecanoic acid .

PA 11 / B.10 comprises 72 mol% of a monomer B.10 (wherein "10" represents sebacic acid with 10 carbon atoms) and 28 mol% of a comonomer formed by the amino-11 acid undecanoic.

These polyamides are prepared according to the method described in the patent document WO2009153534 of page 20 line 12 to page 21 line 9.

- PEBAs used, with PA blocks (respectively homopolyamide B.12, and copolyamide B10 / B.14 or B.12 / B.14 or B.14 / B.18) and PT G blocks: B.12 - PTMG is a PABA with 100% molar blocks of monomer B.12 and PTMG blocks.

B.10 / B.14 - PTMG is a PA block PEBA comprising 50 mol% of B.14 monomer and 50 mol% of B.10 monomer, and PTMG blocks.

B.12 / B.14 - PTMG is a PA block PEBA comprising 50 mol% of B.12 monomer and 50 mol% of B.14 monomer, and PTMG blocks.

B.14 / B.18 - PTMG is a PA block PEBA comprising 50 mol% of B.14 monomer and 50 mol% of B.18 monomer, and PTMG blocks.

If in the examples below the PTMG blocks are generally used as PE blocks, the invention is obviously not limited to this embodiment and it would not depart from the scope of the invention by replacing the PTMG blocks by any other block PE as previously described.

The size of the PA and PE (number-average molecular mass) blocks of the PEBAs are respectively indicated at the top of Table 1 of FIG. 1 under the PEBA used.

The properties of transparency, yellow index and Haze (Table 3) are measured on a 2 mm thick plate.

The properties of resistance to impact of high speed, impact resistance, and flexibility are tested on standard specimens in accordance with the standards used and indicated in Table 1, the chemical resistance properties are measured on IFC test specimens. rubber), the properties of lightness (density) are measured on granules. All these properties are measured respectively according to the standards indicated in Table 1 of Figure 1 and in Tables 2 and 3.

These plates and test pieces are obtained by injection from PEBA granules, optionally dry-blended beforehand with PA granules, of the compositions specified above, and as indicated in Table 1.

Table 1 shows that only Examples 1 to 4 (Ex1 to Ex4) according to the invention combine high transparency and resistance to high speed impact, unlike comparisons 1 to 6 (Cpl to Cp6).

The impact resistance, the chemical resistance, the lightness, and the flexibility of the examples according to the invention are also better than those of the polycarbonate (PC).

The chemical resistance measured by strain deformation (ISO 22088-3 standard, 22h, 23 ° C.) was measured in particular with respect to ethanol and isopropanol. Tables 1 and 2 show chemical resistances conforming to the test specimens of the examples according to the invention, in particular for Ex 2 in PEBA of composition B.12-PTMG (the PA and PE blocks having respective number molecular masses 2000 and 650 g / mol).

Table 2

The use of PEBA according to the invention also has other advantages as shown in Table 3: a less yellow hue (Yi yellow index lower), a lower Haze, and a better transmittance (at 560 nm on plate). 2 mm thick, measured using a Konica-Minolta 3610d spectrophotometer, according to ISO 13468), compared to the respective values found for the shock-enhanced PA B.12: Table 3 Product: Haze Yi Tr% (ASTM (ASTM (560 nm, 2mm, D1003-97) E313-96) ISO 13468)

Ex2 B.12-PTMG 2.2 2.4 91.3

CP2 B.12 reinforced shock 17.7 10.8 82.6

Claims

claims

Use of a copolymer with polyether block (s) and polyamide block (s) for the manufacture of a transparent object, resistant to a high speed impact, and impact resistant, in which said copolymer has the following characteristics:

said PA blocks comprise more than 50 mol%, an equimolar combination of at least one cycloaliphatic diamine and at least one aliphatic dicarboxylic acid having from 12 to 36 carbon atoms,

said PA blocks represent 20 to 90% by weight, relative to the total weight of the copolymer, the number-average molecular mass of the PA blocks is in the range of 1000 to 10000 g / mol,

said PE blocks represent 10 to 80% by weight, based on the total weight of the copolymer,

the number-average molecular mass of the PE blocks is between 200 and 1000 g / mol. 2- Use of a Thermoplastic Polymeric Composition Containing:

from 30 to 99.99% by weight of copolymer according to claim 1,

from 0.01 to 70% by weight of at least one at least partially transparent cycloaliphatic amorphous polyamide,

from 0 to 20% of additives,

on the total weight of the composition,

for the manufacture of a transparent object, resistant to impact of high speed, and impact resistant.

3- Use according to any one of the preceding claims, wherein the object is more transparent and more resistant to a high-speed impact, than an object of the same shape polycarbonate.

4- Use according to claim 3, wherein the object is also more resistant to impact, chemical solvents and lighter than an object of the same form of polycarbonate. 5. Use according to any one of the preceding claims, in which the PA blocks comprise more than 70 mol%, of an equimolar association of at least one cycloaliphatic diamine and of at least one aliphatic, preferably linear, dicarboxylic acid, having from 12 to 18 carbon atoms.

The use as claimed in any one of the preceding claims, wherein said at least one cycloaliphatic diamine is selected from: bis (3,5-dialkyl-4-aminocyclohexyl) methane, bis (3,5-dialkyl) -4- aminocyclohexyl) ethane, bis (3,5-dialkyl-4-aminocyclohexyl) propane, bis (3,5-dialkyl-4-aminocyclohexyl) butane, bis (3-methyl-4-aminocyclohexyl) - methane (BMACM or M ACM), p-bis (aminocyclohexyl) methane (PACM), isopropylidenedi (cyclohexylamine) (PACP), isophoronediamine (IPD), 2,6-bis (amino methyl) norbornane ( BAMN), and their mixtures.

Use according to any one of the preceding claims, wherein said PA block comprises less than 30 mol% of at least one polyamide comonomer different from said equimolar combination of claim 1. 8- Use according to any one of preceding claim, wherein said at least one PE block comprises at least one polyether selected from polyalkylene ether polyols, such as PEG, PPG, PO 3 G, PTMG, polyethers containing polyoxyalkylene sequences with NH 2 chain ends, and random and / or block copolymers, and mixtures thereof.

9- Use according to any one of the preceding claims, wherein the PA blocks are formed essentially (more than 80 mol%) from at least one monomer selected from B.12, B.14, B.16, B.18, their random and / or block copolymers, and mixtures thereof.

10- transparent thermoplastic polymeric composition based on polyamide, said composition comprising: from 30 to 100% by weight of copolymer according to that defined in any one of Claims 1 to 9,

from 0 to 70% by weight of at least one transparent amorphous polyamide which is at least partially cycloaliphatic,

from 0 to 20% of additive,

on the total weight of the composition.

11- Composition according to claim 10, wherein the additive is chosen from: coloring agents, in particular pigments, dyes, effect pigments, such as diffractive pigments, interference pigments, such as pearlescent agents, pigments reflective and their mixtures; anti-UV agents, anti-aging agents, antioxidants; fluidizing agents, anti-abrasion agents, release agents, stabilizers; plasticizers, impact modifiers; surfactants; brighteners; fillers, such as silica, carbon black, carbon nanotubes, expanded graphite, titanium oxide or glass beads; fibers ; waxes; and their mixtures.

12- Use of a composition as defined in one of claims 10 or 11 to form granules or powders.

13- Use of granules as defined in claim 12, for the manufacture of filaments, tubes, films, plates and / or molded objects transparent and resistant to high speed impact. 14- A method of manufacturing a transparent object resistant to a high-speed impact, said method comprising:

a copolymer supplying step according to that defined in any one of claims 1 to 9;

an optional step of mixing said copolymer with at least one transparent amorphous PA and / or at least one additive, so as to manufacture a composition as defined in claim 2; a step of implementing said copolymer or said composition at a temperature T 0 in the range of 90 to 180 ° C .;

a step of recovering the object. 15- Use of a PEBA according to any one of claims 1 to 9 and / or a thermoplastic composition according to any one of claims 10 or 11, for the manufacture of a transparent protective equipment, industrial safety equipment, such as eyeglasses, frames and / or safety glasses, a ballistic window, a transparent impact plate, a helmet, a visor, a shield, a diving suit; sports equipment; a watch glass; space equipment, including satellite, space shuttle; aeronautical equipment, automobile, such as a windshield, a window, a porthole, a cockpit, an aircraft canopy, a window, a bullet-proof glass, for example a car or a construction window, a window projector, lighthouse; a display window, in particular advertising, electronic, computer; a screen element; a panel of thermal, solar, photovoltaic panel; an article in the building, furnishing, appliance and decoration industry; play, toy; fashion, such as shoe heels, jewelry; furniture, such as a table, seat, armchair; an article or presentation element; packaging, case, case; container, flask, perfume article, cosmetic or pharmaceutical industry; a bag ; a protection element during transport.

16- transparent object and resistant to a high speed impact, the composition of which complies with any one of claims 10 or 11.

17- The object of claim 16 having a thickness in the range of 0.1 to 10 mm, preferably 0.1 to 3 mm, preferably 0.5 to 2 mm.

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